Process for producing olefin polymer and olefin polymer

ABSTRACT

[Problem to be solved] 
     There is provided a process for producing an olefin polymer that is capable of producing an olefin polymer having high heat resistance and high molecular weight with excellent catalytic activity. 
     [Solution to problem] 
     The process for producing an olefin polymer includes a step of polymerizing at least one olefin selected from ethylene and α-olefins having 4 to 30 carbon atoms in the presence of an olefin polymerization catalyst containing a transition metal compound represented by the general formula [I], the olefin polymer including constituent units derived from ethylene and α-olefins having 4 to 30 carbon atoms in a total amount between more than 50 mol % and not more than 100 mol %, 
     
       
         
         
             
             
         
       
     
     [in the formula [I], R 1 , R 3  and R 5  to R 16  are each independently a hydrogen atom, a hydrocarbon group or the like; R 2  is a hydrocarbon group or the like; R 4  is a hydrogen atom; M is a transition metal of Group IV; Q is a halogen atom or the like; and j is an integer of 1 to 4].

TECHNICAL FIELD

The present invention relates to processes for producing an olefinpolymer using an olefin polymerization catalyst including a specifictransition metal compound, to olefin polymers obtained by the processes,and to novel 1-butene polymers and 4-methyl-1-pentene polymers.

BACKGROUND ART [Metallocene Compounds]

In recent years, metallocene compounds are well known as homogeneouscatalysts for olefin polymerization. After the report of isotacticpolymerization by W. Kaminsky et al. (see Non Patent Literature 1) ,many studies have been made on olefin polymerization, in particular,stereoregular a-olefin polymerization using metallocene compounds.

In α-olefin polymerization using metallocene compounds, it is known thatthe stereoregularity and the molecular weights of the obtainablea-olefin polymers are greatly varied by the introduction of substituentsinto the cyclopentadienyl ring ligands of the metallocene compounds orby the bridging of the two cyclopentadienyl rings.

[Bridged Metallocene Compounds]

For example, there are the following reports as to propylenepolymerization catalyzed by metallocene compounds which have a ligand inwhich a cyclopentadienyl ring and a fluorenyl ring is bridged to eachother.

From the viewpoint of stereoregularity, dimethylmethylene(cyclopentadienyl) (fluorenyl) zirconium dichloride affords syndiotacticpolypropylene (see Non Patent Literature 2);dimethylmethylene(3-methylcyclopentadienyl) (fluorenyl) zirc oniumdichloride having a methyl group at the 3-position of thecyclopentadienyl ring affords hemiisotactic polypropylene (see PatentLiterature 1); and dimethylmethylene(3-tert-butylcyclopentadienyl)(fluorenyl) zirconium dichloride having a tert-butyl group at the3-position of the cyclopentadienyl ring affords isotactic polypropylene(see Patent Literature 2).

Dimethylmethylene(3-tert-butyl-5-methylcyclopentadien yl)(3,6-di-tert-butylfluorenyl)zirconium dichloride having tert-butylgroups at the 3- and 6-positions of the fluorenyl ring affordspolypropylene with higher isotactic stereoregularity than obtained withdimethylmethylene(3-tert-butyl-5-methylcyclopentadienyl) (fluorenyl)zirconium dichloride (see Patent Literature 3).

From the viewpoint of molecular weights,diphenylmethylene(cyclopentadienyl) (fluorenyl) zirconium dichloridehaving a cyclopentadienyl ring and a fluorenyl ring bridged viadiphenylmethylene affords syndiotactic polypropylene having a highermolecular weight than obtained with dimethylmethylene (cyclopentadienyl)(fluorenyl) zirconium dichloride (see Patent Literature 4);diphenylmethylene(3-(2-adamantyl)-cyclopentadienyl) (fluorenyl)zirconiumdichloride having a diphenylmethylene bridge affordsisotactic-hemiisotactic polypropylene having a higher molecular weightthan obtained with dimethylmethylene (3-(2-adamantyl) -cyclopentadienyl)(fluorenyl)zirconium dichloride (see Non Patent Literature 3); anddimethylmethylene(3-tert-butyl-5-methylcyclopentadienyl) (fluorenyl)zirconium dichloride having a methyl group at the 5-position ofthe cyclopentadienyl ring (the a-position relative to the bridge)affords isotactic polypropylene having a higher molecular weight thanobtained with dimethylmethylene(3-tert-butylcyclopentadienyl)(fluorenyl) zirconium dichloride (see Patent Literature 5).

Further, dimethylmethylene(3-tert-butyl-2-methylcyclopentadienyl) (fluorenyl)zirconium dichloride and diphenylmethylene(3,4-dimethylcyclopentadienyl) (fluorenyl) zirconium dichloride havingsubstituents at two adjacent positions on the cyclopentadienyl ringafford polypropylene having a lower molecular weight than obtained withdimethylmethylene(3-tert-butyl-5-methylcyclopentadienyl) (fluorenyl)zirconium dichloride anddiphenylmethylene(3-methylcyclopentadienyl) (fluorenyl) zirc oniumdichloride, respectively (see Patent Literatures 5 and 6).

[5-Membered Ring-Bridged Metallocene Compounds]

A study reports the polymerization of propylene catalyzed by ametallocene compound in which a cyclopentadienyl ring and a fluorenylring are bridged via a 5-membered ring. However, such metallocenecompounds have low usefulness in industry because of the fact that thestereoregularity of the obtainable polypropylenes is very low (see NonPatent Literature 4).

A recent study reports a metallocene compound having a cyclopentadienylring and a fluorenyl ring bridged via a 5-membered ring which can affordpolypropylene having relatively high stereoregularity (see PatentLiterature 7).

These metallocene compounds mentioned above exhibit excellentpolymerization performance. In some applications, however, the catalystsare often required to afford polymers having still higherstereoregularity or still higher molecular weight with higher economicefficiency, namely, with high catalytic activity even underhigh-temperature polymerization conditions. Improvements are thusrequired.

[Metallocene Compounds Having Substituted Indenyl Ligands]

According to reports, metallocene compounds having substituted indenylligands afford relatively high stereoregularity or molecular weight (seePatent Literatures 8 and 9). However, such compounds are unsatisfactoryin terms of performance under economically efficient polymerizationconditions.

Because metallocene compounds are soluble in reaction media, they aregenerally used to catalyze polymerization in the form of supportedcatalyst systems in slurry polymerization or gas phase polymerization.Specifically, the metallocene compounds are supported on solid carriers.However, it is known that the polymerization performances such asstereoregularity control of the aforementioned compounds are markedlydecreased when they are used in the supported form on carriers ascompared to in the absence of carriers.

[Metallocene Compounds Having Substituted Azulenyl Groups]

To solve such problems, for example, a recent study reports ametallocene compound having a substituted azulenyl group as a ligand(see Patent Literature 10). However, even such catalysts do not achievesufficient performances such as stereoregularity control when thepolymerization temperature is elevated to obtain economic efficiency orwhen the compounds are supported on solid carriers.

Under these circumstances, there have been demands for furtherimprovements in the catalytic performances such as polymerizationactivity, stereoregularity control and molecular weight control ofpolymerization catalysts including metallocene compounds (hereinafter,also written as “metallocene catalysts”).

[Reports of Polymerization Using Metallocene Catalysts]

Regarding the polymerization of monomers other than propylene with useof metallocene catalysts, for example, there are studies reporting thepolymerization of 1-butene catalyzed by a metallocene compound having anindene ring as a ligand (see Patent Literatures 11 and 12).

Further, the polymerization of 1-butene catalyzed by a metallocenecompound having a fluorene ring as a ligand has been reported.Specifically, the polymerization usingisopropylidene(3-t-butyl-5-methylcyclopentadienyl) (fluorenyl)zirconiumdichloride has been disclosed (see Patent Literature 13). According tothis report, the obtainable polybutene has lower regioirregularity dueto 4,1-insertions and exhibits higher heat resistance and mechanicalstrength as compared to when the polymerization is catalyzed by ametallocene compound having an indene ring as a ligand. In someapplications, however, the catalysts are often required to affordpolymers having still higher stereoregularity or still higher molecularweight under more economically efficient conditions. Improvements arethus required.

A study reports the polymerization of 4-methyl-1-pentene as a mainmonomer (see Patent Literature 14). Patent Literature 14 describes thatmetallocene-catalyzed polymers outperform conventionalZiegler-Natta-catalyzed polymers in the balance of properties such asheat resistance and are thus highly useful in industry. However,applications sometimes require that the polymers have a still highermelting point/stereoregularity or have a still higher molecular weight.

In general, increasing the polymerization temperature enhances economicefficiency but at the same time tends to decrease the molecular weightor the melting point/stereoregularity of the obtainable polymers. Thus,there have been demands for the development of novel polymerizationprocesses capable of producing polymers having a higher molecular weightand a higher melting point/higher stereoregularity.

CITATION LIST Patent Literature

Patent Literature 1: JP-A-H03-193796

Patent Literature 2: JP-A-H06-122718

Patent Literature 3: WO 2001/027124

Patent Literature 4: JP-A-H02-274703

Patent Literature 5: JP-A-2001-526730

Patent Literature 6: JP-A-H10-226694

Patent Literature 7: WO 2006/068308

Patent Literature 8: JP-A-H04-268304

Patent Literature 9: JP-A-H06-157661

Patent Literature 10: JP-A-2003-292518

Patent Literature 11: WO 2004/099269

Patent Literature 12: WO 2004/050724

Patent Literature 13: JP-A-2010-150433

Patent Literature 14: WO 2005/121192

Non Patent Literature

Non Patent Literature 1: Angew. Chem. Int. Ed. Engl., 24, 507 (1985)

Non Patent Literature 2: J. Am. Chem. Soc., 110, 6255 (1988)

Non Patent Literature 3: Organometallics, 21, 934 (2002)

Non Patent Literature 4: Metalorganic Catalysts for Synthesis andPolymerization, Springer-Verlag: Berlin, 1999; p. 170.

SUMMARY OF INVENTION Technical Problem

An object of the invention is to provide olefin polymer productionprocesses capable of producing olefin polymers having high heatresistance and high molecular weight with excellent catalytic activity,and to provide olefin polymers obtained by the processes. Another objectof the invention is to provide novel 1-butene polymers having high heatresistance and high molecular weight, for example, 1-butene polymershaving an excellent balance between rigidity and yield stress. A furtherobject of the invention is to provide novel 4-methyl-1-pentene polymers,for example, crystalline 4-methyl-1-pentene polymers having an excellentbalance between rigidity and toughness, and amorphous or low-crystalline4-methyl-1-pentene polymers having an excellent balance in viscoelasticproperties.

Solution to Problem

The present inventors carried out extensive studies to achieve the aboveobjects. As a result, the present inventors have found that the objectsmay be achieved by using olefin polymerization catalysts which include atransition metal compound having a configuration described below, or maybe achieved with 1-butene polymers and 4-methyl-1-pentene polymershaving configurations described below. The present invention has beencompleted based on the finding.

An aspect of the present invention resides in a process for producing anolefin polymer including a step of polymerizing at least one olefinselected from ethylene and α-olefins having 4 to 30 carbon atoms, andpropylene as needed, in the presence of an olefin polymerizationcatalyst including at least one transition metal compound (A) selectedfrom transition metal compounds represented by the general formula [I]and enantiomers thereof, the olefin polymer including constituent unitsderived from the at least one selected from ethylene and a-olefinshaving 4 to 30 carbon atoms in a total amount between more than 50 mol %and not more than 100 mol %, and constituent units derived frompropylene in an amount between 0 mol % and less than 50 mol % (whereinthe content of the constituent units derived from ethylene and a-olefinshaving 4 to 30 carbon atoms and the content of the constituent unitsderived from propylene total 100 mol %).

[In the formula [I], R¹, R³, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R₁₂, R₁₃,R₁₄, R¹⁵ and R¹⁶ are each independently a hydrogen atom, a hydrocarbongroup, a hetero atom-containing hydrocarbon group, or asilicon-containing group; R² is a hydrocarbon group, a heteroatom-containing hydrocarbon group, or a silicon-containing group; R⁴ isa hydrogen atom; any two substituents of the substituents R¹ to R¹⁶except R⁴ may be bonded to each other to form a ring; M is a transitionmetal of Group IV; Q is a halogen atom, a hydrocarbon group, an anionicligand, or a neutral ligand coordinatable with a lone electron pair; jis an integer of 1 to 4; and when j is an integer of 2 or greater, Qsmay be the same or different from one another].

In the general formula [I], R¹ and R³ are preferably hydrogen atoms; R²is preferably a hydrocarbon group having 1 to 20 carbon atoms; R² ispreferably a substituent in which a carbon bonded to thecyclopentadienyl ring is a tertiary carbon; R⁵ and R⁷ are preferablybonded to each other to form a ring; R⁹, R¹², R¹³ and R¹⁶ are preferablyhydrogen atoms; and R¹⁰, R¹¹ are R¹⁴ and R¹⁵ are preferably hydrocarbongroups, or R¹⁰ and R¹¹ are preferably bonded to each other to form aring and R¹⁴ and R¹⁵ are preferably bonded to each other to form a ring.

Preferably, the olefin polymerization catalyst further includes at leastone compound (B) selected from (B-1) organometallic compounds, (B-2)organoaluminum-oxy compounds, and (B-3) compounds that react with thetransition metal compound (A) to form an ion pair.

Preferably, the olefin polymerization catalyst further includes acarrier (C), and the transition metal compound (A) that is supported onthe carrier (C) is used.

Another aspect of the invention resides in an olefin polymer obtained bythe above production process. The olefin polymer is preferably a1-butene polymer or a 4-methyl-1-pentene polymer.

Another aspect of the invention resides in a 1-butene polymer which hasa meso pentad fraction as measured by ¹³C-NMR of 98.0% to 99.8%.

In the 1-butene polymer, it is preferable that the accumulated elutionamount at a temperature [T_(X)] be 40% by weight or more relative to thewhole elution amount as measured by cross fractionation chromatography(CFC) using o-dichlorobenzene as an eluent, provided that [T_(X)] isdefined as ([T_(S)]+[T_(E)])/2 wherein [T_(S)] is an elution starttemperature (a temperature at which the accumulated elution weightpercent reaches 0.5% by weight), and [Ts] is an elution end temperature(a temperature at which the accumulated elution weight percent reaches99% by weight).

Another aspect of the invention resides in a 4-methyl-1-pentene polymerfulfilling the following requirements (a) to (c):

-   -   (a) the amount of constituent units derived from        4-methyl-1-pentene is 100 to 80 mol %, and the amount of        constituent units derived from at least one selected from        olefins having 2 to 30 carbon atoms (except 4-methyl-1-pentene)        is 0 to 20 mol %;    -   (b) the meso diad fraction (m) as measured by ¹³C-NMR is 98.5%        to 100%; and    -   (c) the heat of fusion ΔHm (unit: J/g) and the melting point Tm        (unit: ° C.) as measured by Differential Scanning calorimetry        (DSC) fulfill the following relation (1):

Relation (1): ΔHm≧0.5×Tm−76.

Another aspect of the invention resides in a 4-methyl-1-pentene polymerfulfilling the following requirements (d) to (f):

-   -   (d) the amount of constituent units derived from        4-methyl-1-pentene is more than 50 mol % and less than 80 mol %,        and the amount of constituent units derived from at least one        selected from olefins having 2 to 30 carbon atoms (except        4-methyl-1-pentene) is more than 20 mol % and less than 50 mol        %;    -   (e) the meso diad fraction (m) as measured by ¹³C-NMR is 98.5%        to 100%; and    -   (f) the melting point Tm as measured by Differential Scanning        calorimetry (DSC) is lower than 100° C. or is substantially        absent.

Advantageous Effects Of Invention

According to the present invention, there may be provided olefin polymerproduction processes capable of producing olefin polymers having highheat resistance and high molecular weight with excellent catalyticactivity, and further may be provided olefin polymers obtained by theprocesses. Further, the invention can provide novel 1-butene polymershaving high heat resistance and high molecular weight, for example,1-butene polymers having an excellent balance between rigidity and yieldstress. Furthermore, the invention can provide novel 4-methyl-1-pentenepolymers, for example, crystalline 4-methyl-1-pentene polymers having anexcellent balance between rigidity and toughness, and amorphous orlow-crystalline 4-methyl-1-pentene polymers having an excellent balancein viscoelastic properties.

BRIEF DESCRIPTION OF DRAWINGS

FIG. 1A is a graph illustrating a CFC elution curve of a 1-butenepolymer obtained in Example, and FIG. 1B is a graph illustrating a CFCelution curve of a 1-butene polymer obtained in Comparative Example.

FIG. 2 is a graph which plots the Young's modulus of crystalline4-methyl-1-pentene polymers obtained in Examples and ComparativeExamples versus elongation at break.

FIG. 3 is a graph which plots the heat of fusion ΔHm of crystalline4-methyl-1-pentene polymers obtained in Examples and ComparativeExamples versus melting point Tm. The straight line on the graphindicates ΔHm=0.5×Tm−76.

DESCRIPTION OF EMBODIMENTS

Hereinbelow, there will be sequentially described transition metalcompounds represented by the general formula [I] and enantiomers thereofused in production processes of the invention, processes for producingsuch compounds, olefin polymerization catalysts including at least oneof such compounds, olefin polymer production processes using the olefinpolymerization catalyst, olefin polymers, and shaped articles includingthe olefin polymer.

In the specification, compounds represented by formula (X) (X: formulanumber) are also written as “compounds (X)”. In the description ofpolymers, constituent units derived from compound A are also written as“compound A units”, and the content thereof may be written as “compoundA content”.

[Transition Metal Compounds (A)]

The transition metal compound (A) used in the invention is at least oneselected from transition metal compounds represented by the generalformula [I] and enantiomers thereof. Although the specification does notspecifically mention the enantiomers, the transition metal compounds (A)include all the enantiomers of the transition metal compounds [I], forexample, transition metal compounds represented by the general formula[I′], without departing from the spirit of the invention.

In the formula [I], R¹, R³, R⁵, R⁶, R⁷, R₈, R₉, R¹⁰, R¹¹, R₁₂, R₁₃, R₁₄,R¹⁵ and R¹⁶ are each independently a hydrogen atom, a hydrocarbon group,a hetero atom-containing hydrocarbon group, or a silicon-containinggroup; R² is a hydrocarbon group, a hetero atom-containing hydrocarbongroup, or a silicon-containing group; R⁴ is a hydrogen atom; and any twosubstituents of the substituents R¹ to R¹⁶ except R⁴ maybe bonded toeach other to form a ring.

In the formula [I], M is a transition metal of Group IV; Q is a halogenatom, a hydrocarbon group, an anionic ligand, or a neutral ligandcoordinatable with a lone electron pair; j is an integer of 1 to 4; andwhen j is an integer of 2 or greater, Qs may be the same or differentfrom one another.

In the formulae [I] and [I′], the MQ_(j) moiety comes out of the planeof the paper, and the bridge goes back behind the plane of the paper.Specifically, the transition metal compounds (A) are such that thehydrogen atom (R⁴) is bonded to the α-position relative to thecyclopentadiene ring (relative to the carbon atom substituted with thebridge) on the same side as the central metal.

The transition metal compounds [I] are such that R² is not a hydrogenatom and R⁴ is a hydrogen atom. This configuration removes thedifficulties encountered with the conventional metallocene compounds inproducing olefin polymers which have high stereoregularity and a highmelting point and further have a high molecular weight even undereconomically efficient polymerization conditions.

The reasons why the transition metal compounds [I] exhibit excellentperformance will be explained based on an estimated polymerizationmechanism below. As an example, the influence on the molecular weightsof polymers will be discussed.

Polymerization reaction produces a polymer having a high molecularweight when the insertion of a monomer between a central metal of acatalyst and a polymer chain, namely, the growth reaction takes place ata much higher rate than chain transfer reaction which stops the growthof the polymer chain. Two main chain transfer reactions that are knownin metallocene-catalyzed olefin polymerization reaction are β-hydrogentransfer in which a hydrogen atom transfers to a central metal M of acatalyst, and β-hydrogen transfer in which a hydrogen atom transfers toa monomer, and the latter β-hydrogen transfer is said to be the maindominant transfer (see, for example, Chem. Rev. (2000), 100, 1253).

Transition states of these transfers are schematically illustrated inthe formulae (i) to (iii). Ligands of the catalyst are omitted. In theformulae (i) to (iii), M′ represents the active central metal of thecatalyst, and P indicates the polymer chain.

The structure in the transition state in the β-hydrogen transfer to themonomer is an M′-centered, six-membered ring structure (formula (ii)).In the monomer insertion reaction, a five-membered ring structure isformed as a result of the coordination of the a-hydrogen to M′ (formula(i)). The narrowing of the space near M′ by the ligands of the catalystrenders the six-membered ring structure in the transition staterequiring a larger space less stable than the five-membered ringstructure in the transition state. That is, the reaction rate of theβ-hydrogen transfer to the monomer is decreased, and the reaction rateof the insertion of the monomer is relatively increased. As a result,the molecular weight of the resultant polymer is increased (seeMacromolecules (1996), 29, 2729).

On the other hand, the structure in the transition state in theβ-hydrogen transfer to the central metal M is a four-membered ringstructure (formula (iii)) occupying a smaller space than the structurein the transition state in the monomer insertion reaction. As a result,excessive narrowing of the space near M′ by the ligands will cause arelative increase in the reaction rate of the β-hydrogen transfer to thecentral metal M, and consequently the molecular weight of the resultantpolymer is expected to be low.

The above reaction mechanism is applied to the transition metal compound[I]. The transition metal compound [I] has a five-membered ringstructure as the bridge between the cyclopentadiene ring and thefluorene ring. If the skeleton is such that R² is not a hydrogen atomand R⁴ is a substituent larger than a hydrogen atom, namely, asubstituent other than a hydrogen atom, the space near the central metalM is narrowed.

Although such a structure may suppress the β-hydrogen transfer to themonomer which proceeds via the transition state with the six-memberedring structure, it is probable that the reaction rate of the monomerinsertion reaction via the transition state with the five-membered ringstructure will be decreased at the same time. As a result, theβ-hydrogen transfer to the central metal M via the transition state withthe four-membered ring structure is promoted, and the polymer is notgrown to a sufficiently high molecular weight.

In contrast, a skeleton in which R² is not a hydrogen atom and R⁴ is ahydrogen atom is considered to be able to suppress the β-hydrogentransfer to the monomer alone without inhibiting the monomer insertionreaction, and consequently the polymer may be grown to a highermolecular weight.

The mechanism described above is probably the reason why the catalystexhibits excellent performance only when the bridge between thecyclopentadiene ring and the fluorene ring includes a five-membered ringstructure and R² is not a hydrogen atom while R⁴ is a hydrogen atom.

<R⁴ to R⁴⁶>

Examples of the hydrocarbon groups represented by any of R¹ to R¹⁶(except R⁴) include linear hydrocarbon groups, branched hydrocarbongroups, cyclic saturated hydrocarbon groups, cyclic unsaturatedhydrocarbon groups, and groups resulting from the substitution of one,or two or more hydrogen atoms in saturated hydrocarbon groups withcyclic unsaturated hydrocarbon groups. The number of carbon atoms in thehydrocarbon groups is usually 1 to 20, preferably 1 to 15, and morepreferably 1 to 10.

Examples of the linear hydrocarbon groups include linear alkyl groupssuch as methyl group, ethyl group, n-propyl group, n-butyl group,n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonylgroup and n-decanyl group; and linear alkenyl groups such as allylgroup.

Examples of the branched hydrocarbon groups include branched alkylgroups such as isopropyl group, tert-butyl group, tert-amyl group,3-methylpentyl group, 1,1-diethylpropyl group, 1,1-dimethylbutyl group,1-methyl-1-propylbutyl group, 1,1-propylbutyl group,1,1-dimethyl-2-methylpropyl group and1-methyl-1-isopropyl-2-methylpropyl group.

Examples of the cyclic saturated hydrocarbon groups include cycloalkylgroups such as cyclopentyl group, cyclohexyl group, cycloheptyl group,cyclooctyl group and methylcyclohexyl group; and polycyclic groups suchas norbornyl group, adamantyl group and methyladamantyl group.

Examples of the cyclic unsaturated hydrocarbon groups include arylgroups such as phenyl group, tolyl group, naphthyl group, biphenylgroup, phenanthryl group and anthracenyl group; cycloalkenyl groups suchas cyclohexenyl group; and polycyclic unsaturated alicyclic groups suchas 5-bicyclo[2.2.1]hept-2-enyl group.

Examples of the groups resulting from the substitution of one, or two ormore hydrogen atoms in saturated hydrocarbon groups with cyclicunsaturated hydrocarbon groups include groups resulting from thesubstitution of one, or two or more hydrogen atoms in alkyl groups witharyl groups, such as benzyl group, cumyl group, 1,1-diphenylethyl groupand triphenylmethyl group.

Examples of the hetero atom-containing hydrocarbon groups represented byany of R¹ to R¹⁶ (except R⁴) include oxygen atom-containing hydrocarbongroups, for example, alkoxy groups such as methoxy group and ethoxygroup, aryloxy groups such as phenoxy group, and furyl group; nitrogenatom-containing hydrocarbon groups, for example, amino groups such asN-methylamino group, N,N-dimethylamino group and N-phenylamino group,and pyrryl group; and sulfur atom-containing hydrocarbon groups, forexample, thienyl group. The number of carbon atoms in the heteroatom-containing hydrocarbon groups is usually 1 to 20, preferably 2 to18, and more preferably 2 to 15. Silicon-containing groups are excludedfrom the hetero atom-containing hydrocarbon groups.

Examples of the silicon-containing groups represented by any of R¹ toR¹⁶ (except R⁴) include groups represented by -SiR₃ (wherein Rs are eachindependently an alkyl group having 1 to 15 carbon atoms or a phenylgroup), such as trimethylsilyl group, triethylsilyl group,dimethylphenylsilyl group, diphenylmethylsilyl group and triphenylsilylgroup.

Of the substituents R¹ to R¹⁶ except R⁴, any two adjacent substituents(for example: R¹ and R², R² and R³, R⁵ and R⁷, R⁶ and R⁸, R⁷ and R⁸, R⁹and R¹⁰, R¹⁰ and R¹¹, R¹¹ and R¹², R²³ and R¹⁴, R¹⁴ and R¹⁵, and R¹⁵ andR¹⁶) may be bonded to each other to form a ring. R⁶ and R⁷ may be bondedto each other to form a ring, R¹ and R⁸ may be bonded to each other toform a ring, and R³ and R⁵ may be bonded to each other to form a ring.Two or more such rings may be present in the molecule.

In the specification, examples of the rings formed by the bonding of twosubstituents (the additional rings) include alicyclic rings, aromaticrings and hetero rings. Specific examples include a cyclohexane ring; abenzene ring; a hydrogenated benzene ring; a cyclopentene ring; andhetero rings such as a furan ring and a thiophene ring, andcorresponding hydrogenated hetero rings. A cyclohexane ring; and abenzene ring and a hydrogenated benzene ring are preferable. Such a ringstructure may further have a substituent such as an alkyl group on thering.

From the viewpoint of stereoregularity control, R¹ and R³ are preferablyhydrogen atoms.

At least one selected from R⁵, R⁶ and R⁷ is preferably a hydrocarbongroup, a hetero atom-containing hydrocarbon group or asilicon-containing group. It is more preferable that R⁵ be a hydrocarbongroup. R⁵ is more preferably an alkyl group having 2 or more carbonatoms such as a linear alkyl group or a branched alkyl group, or acycloalkyl group or a cycloalkenyl group. Particularly preferably, R⁵ isan alkyl group having 2 or more carbon atoms. From the viewpoint ofsynthesis, it is also preferable that R⁶ and R⁷ be hydrogen atoms. Morepreferably, R⁵ and R⁷ are bonded to each other to form a ring, and thering is particularly preferably a six-membered ring such as acyclohexane ring.

R⁸ is preferably a hydrocarbon group, and is particularly preferably analkyl group.

From the viewpoint of stereoregularity control, R² is preferably ahydrocarbon group, more preferably a hydrocarbon group having 1 to 20carbon atoms, still more preferably a hydrocarbon group other than arylgroups, further preferably a linear hydrocarbon group, a branchedhydrocarbon group or a cyclic saturated hydrocarbon group, andparticularly preferably a substituent in which the free valence carbon(the carbon bonded to the cyclopentadienyl ring) is tertiary carbon.

Specific examples of R² include methyl group, ethyl group, isopropylgroup, tert-butyl group, tert-pentyl group, tert-amyl group,1-methylcyclohexyl group and 1-adamantyl group. More preferredsubstituents are those in which the free valence carbon is tertiarycarbon, such as tert-butyl group, tert-pentyl group, 1-methylcyclohexylgroup and 1-adamantyl group. Particularly preferred substituents aretert-butyl group and 1-adamantyl group.

In the general formula [I], the fluorene ring moiety is not particularlylimited as long as the structure is formed of a known fluorenederivative. From the viewpoint of the controlling of stereoregularityand molecular weight, however, it is preferable that R⁹, R¹², R¹³ andR¹⁶ be hydrogen atoms.

R¹⁰, R¹¹, R¹⁴ and R¹⁵ are preferably hydrogen atoms, hydrocarbon groups,oxygen atom-containing hydrocarbon groups or nitrogen atom-containinghydrocarbon groups, more preferably hydrocarbon groups, and still morepreferably hydrocarbon groups having 1 to 20 carbon atoms.

R¹⁰ and R¹¹ may be bonded to each other to form a ring, and R¹⁴ and R¹⁵may be bonded to each other to form a ring.

Examples of such substituted fluorenyl groups include benzofluorenylgroup, dibenzofluorenyl group, octahydrodibenzofluorenyl group,1,1,4,4,7,7,10,10-octamethyl-2,3,4,7,8,9,10,12-octahydro-1 H-dibenzo[b,h]fluorenyl group,1,1,3,3,6,6,8,8-octamethyl-2,3,6,7,8,10-hexahydro-1H-dicyclopenta[b,h]fluorenyl group and 1′, 1′, 3′, 6′, 8′,8′-hexamethyl-1′H,8′H-dicyclopenta[b,h]fluorenyl group, with1,1,4,4,7,7,10,10-octamethyl-2,3,4,7,8,9,10,12-octahydro-1H-dibenzo[b,h]fluorenyl group being particularly preferable.

<M, Q and j>

M is a Group IV transition metal, preferably Ti, Zr or Hf, morepreferably Zr or Hf, and particularly preferably Zr.

Examples of the halogen atoms which may be represented by Q includefluorine, chlorine, bromine and iodine.

Examples of the hydrocarbon groups which may be represented by Q includegroups similar to the hydrocarbon groups represented by any of R¹ to R¹⁶(except R⁴), with alkyl groups such as linear alkyl groups and branchedalkyl groups being preferable.

Examples of the anionic ligands which may be represented by Q includealkoxy groups such as methoxy and tert-butoxy; aryloxy groups such asphenoxy; carboxylate groups such as acetate and benzoate; sulfonategroups such as mesylate and tosylate; and amide groups such asdimethylamide, diisopropylamide, methylanilide and diphenylamide.

Examples of the neutral ligands coordinatable with a lone electron pairwhich may be represented by Q include organophosphorus compounds such astrimethylphosphine, triethylphosphine, triphenylphosphine anddiphenylmethylphosphine; and ethers such as tetrahydrofuran, diethylether, dioxane and 1,2-dimethoxyethane.

It is preferable that at least one Q be a halogen atom or an alkylgroup.

The letter j is preferably 2.

Some preferred embodiments of the configurations of the transition metalcompounds [I], namely, R¹ to R¹⁶, M, Q and j are described hereinabove.In the invention, any combinations of these preferred embodiments arealso preferable.

<Examples of Preferred Transition Metal Compounds>

In the following examples,1,1,4,4,7,7,10,10-octamethyl-2,3,4,7,8,9,10,12-octahydro-1H-dibenzo[b,h]fluorene is written as octamethylfluorene, and1′,1′,3′,6′,8′,8′-hexamethyl-1′H,8′H-dicyclopenta[b,h]fluorene ashexamethyldicyclopentafluorene.

Preferred examples of the transition metal compound used in the presentinvention include: [1-(fluorene-9′-yl)(1,2,3,4-tetrahydropentalene)]zirconiumdichloride,[1-(2′,7′-di-tert-butylfluorene-9′-yl)(1,2,3,4-tetrahydropentalene)]zirconiumdichloride,[1-(3′,6′-di-tert-butylfluorene-9′-yl)(1,2,3,4-tetrahydropentalene)]zirconiumdichloride,[1-(3′,6′-di-(1-adamantyl)-fluorene-9′-yl)(1,2,3,4-tetrahydropentalene)]zirconiumdichloride,[1-(3′,6′-di-tert-butyl-2′,7′-dimethylfluorene-9′-yl)(1,2,3,4-tetrahydropentalene)]zirconiumdichloride,[1-(octamethylfluorene-12′-yl)(1,2,3,4-tetrahydropentalene)]zirconiumdichloride,[1-(hexamethyldicyclopentafluorene-10′-yl)(1,2,3,4-tetrahydropentalene)]zirconiumdichloride, [1-(fluorene-9′-yl)(5-tert-butyl-1-methyl-1,2,3,4-tetrahydropentalene)]zirconiumdichloride,[1-(2′,7′-di-tert-butylfluorene-9′-yl)(5-tert-butyl-1-methyl-1,2,3,4-tetrahydropentalene)]zirconiumdichloride,[1-(3′,6′-di-tert-butylfluorene-9′-yl)(5-tert-butyl-1-methyl-1,2,3,4-tetrahydropentalene)]zirconiumdichloride,[1-(3′,6′-di-(1-adamantyl)-fluorene-9′-yl)(5-tert-butyl-1-methyl-1,2,3,4-tetrahydropentalene)]zirconiumdichloride,[1-(3′,6′-di-tert-butyl-2′,7′-dimethylfluorene-9′-yl)(5-tert-butyl-1-methyl-1,2,3,4-tetrahydropentalene)]zirconiumdichloride,[1-(octamethylfluorene-12′-yl)(5-tert-butyl-1-methyl-1,2,3,4-tetrahydropentalene)]zirconiumdichloride,[1-(hexamethyldicyclopentafluorene-10′-yl)(5-tert-butyl-1-methyl-1,2,3,4-tetrahydropentalene)]zirconiumdichloride,[1-(fluorene-9′-yl)(5-tert-butyl-1-phenyl-1,2,3,4-tetrahydropentalene)]zirconiumdichloride,[1-(2′,7′-di-tert-butylfluorene-9′-yl)(5-tert-butyl-1-phenyl-1,2,3,4-tetrahydropentalene)]zirconiumdichloride,[1-(3′,6′-di-tert-butylfluorene-9′-yl)(5-tert-butyl-1-phenyl-1,2,3,4-tetrahydropentalene)]zirconiumdichloride,[1-(3′,6′-di-(1-adamantyl)-fluorene-9′-yl)(5-tert-butyl-1-phenyl-1,2,3,4-tetrahydropentalene)]zirconiumdichloride,[1-(3′,6′-di-tert-butyl-2′,7′-dimethylfluorene-9′-yl)(5-tert-butyl-1-phenyl-1,2,3,4-tetrahydropentalene)]zirconiumdichloride,[1-(octamethylfluorene-12′-yl)(5-tert-butyl-1-phenyl-1,2,3,4-tetrahydropentalene)]zirconiumdichloride,[1-(hexamethyldicyclopentafluorene-10′-yl)(5-tert-butyl-1-phenyl-1,2,3,4-tetrahydropentalene)]zirconiumdichloride,[1-(fluorene-9′-yl)(5-adamantane-1-yl-1-methyl-1,2,3,4-tetrahydropentalene)]zirconiumdichloride,[1-(2′,7′-di-tert-butylfluorene-9′-yl)(5-adamantane-1-yl-1-methyl-1,2,3,4-tetrahydropentalene)]zirconiumdichloride,[1-(3′,6′-di-tert-butylfluorene-9′-yl)(5-adamantane-1-yl-1-methyl-1,2,3,4-tetrahydropentalene)]zirconiumdichloride,[1-(3′,6′-di-(1-adamantyl)-fluorene-9′-yl)(5-adamantane-1-yl-1-methyl-1,2,3,4-tetrahydropentalene)]zirconiumdichloride,[1-(3′,6′-di-tert-butyl-2′,7′-dimethylfluorene-9′-yl)(5-adamantane-1-yl-1-methyl-1,2,3,4-tetrahydropentalene)]zirconiumdichloride,[1-(octamethylfluorene-12′-yl)(5-adamantane-1-yl-1-methyl-1,2,3,4-tetrahydropentalene)]zirconiumdichloride,[1-(hexamethyldicyclopentafluorene-10′-yl)(5-adamantane-1-yl-1-methyl-1,2,3,4-tetrahydropentalene)]zirconiumdichloride,[1-(fluorene-9′-yl)(5-(1-methylcylohexyl)-1-methyl-1,2,3,4-tetrahydropentalene)]zirconiumdichloride,[1-(2′,7′-di-tert-butylfluorene-9′-yl) (5-(1-methylcylohexy1)-1-methyl-1,2,3,4-tetrahydropentalene)]zirconiumdichloride,[1-(3′,6′-di-tert-butylfluorene-9′-yl) (5-(1-methylcylohexy1)-1-methyl-1,2,3,4-tetrahydropentalene)]zirconiumdichloride,[1-(3′,6′-di-(1-adamantyl)-fluorene-9′-yl)(5-(1-methylcylohexyl)-1-methyl-1,2,3,4-tetrahydropentalene)]zirconiumdichloride,[1-(3′,6′-di-tert-butyl-2′,7′-dimethylfluorene-9′-yl)(5-(1-methylcylohexyl)-1-methyl-1,2,3,4-tetrahydropentalene)]zirconiumdichloride,[1-(octamethylfluorene-12′-yl)(5-(1-methylcylohexyl)-1-methyl-1,2,3,4-tetrahydropentalene)]zirconiumdichloride,[1-(hexamethyldicyclopentafluorene-10′-yl)(5-(1-methylcylohexyl)-1-methyl-1,2,3,4-tetrahydropentalene)]zirconiumdichloride,[1-(fluorene-9′-yl)(5-tert-butyl-1-ethyl-1,2,3,4-tetrahydropentalene)]zirconiumdichloride,[1-(2′,7′-di-tert-butylfluorene-9′-yl)(5-tert-butyl-1-ethyl-1,2,3,4-tetrahydropentalene)]zirconiumdichloride,[1-(3′,6′-di-tert-butylfluorene-9′-yl)(5-tert-butyl-1-ethyl-1,2,3,4-tetrahydropentalene)]zirconiumdichloride,[1-(3′,6′-di-(1-adamantyl)-fluorene-9′-yl)(5-tert-butyl-1-ethyl-1,2,3,4-tetrahydropentalene)]zirconiumdichloride,[1-(3′,6′-di-tert-butyl-2′,7′-dimethylfluorene-9′-yl)(5-tert-butyl-1-ethyl-1,2,3,4-tetrahydropentalene)]zirconiumdichloride,[1-(octamethylfluorene-12′-yl)(5-tert-butyl-1-ethyl-1,2,3,4-tetrahydropentalene)]zirconiumdichloride,[1-(hexamethyldicyclopentafluorene-10′-yl)(5-tert-butyl-1-ethyl-1,2,3,4-tetrahydropentalene)]zirconiumdichloride,[1-(fluorene-9′-yl)(5-tert-butyl-1-iso-propyl-1,2,3,4-tetrahydropentalene)]zirconiumdichloride,[1-(2′,7′-di-tert-butylfluorene-9′-yl)(5-tert-butyl-1-iso-propyl-1,2,3,4-tetrahydropentalene)]zirconiumdichloride,[1-(3′,6′-di-tert-butylfluorene-9′-yl)(5-tert-butyl-1-iso-propyl-1,2,3,4-tetrahydropentalene)]zirconiumdichloride,[1-(3′,6′-di-(1-adamantyl)-fluorene-9′-yl)(5-tert-butyl-1-iso-propyl-1,2,3,4-tetrahydropentalene)]zirconiumdichloride,[1-(3′,6′-di-tert-butyl-2′,7′-dimethylfluorene-9′-yl)(5-tert-butyl-1-iso-propyl-1,2,3,4-tetrahydropentalene)]zirconiumdichloride,[1-(octamethylfluorene-12′-yl)(5-tert-butyl-1-iso-propyl-1,2,3,4-tetrahydropentalene)]zirconiumdichloride,[1-(hexamethyldicyclopentafluorene-10′-yl)(5-tert-butyl-1-iso-propyl-1,2,3,4-tetrahydropentalene)]zirconiumdichloride,[1-(fluorene-9′-yl)(5-adamantane-1-yl-1-iso-propyl-1,2,3,4-tetrahydropentalene)]zirconiumdichloride,[1-(2′,7′-di-tert-butylfluorene-9′-yl)(5-adamantane-1-yl-1-iso-propyl-1,2,3,4-tetrahydropentalene)]zirconiumdichloride,[1-(3′,6′-di-tert-butylfluorene-9′-yl)(5-adamantane-1-yl-1-iso-propyl-1,2,3,4-tetrahydropentalene)]zirconiumdichloride,[1-(3′,6′-di-(1-adamantyl)-fluorene-9′-yl)(5-adamantane-1-yl-1-iso-propyl-1,2,3,4-tetrahydropentalene)]zirconiumdichloride,[1-(3′,6′-di-tert-butyl-2′,7′-dimethylfluorene-9′-yl)(5-adamantane-1-yl-1-iso-propyl-1,2,3,4-tetrahydropentalene)]zirconiumdichloride,[1-(octamethylfluorene-12′-yl)(5-adamantane-1-yl-1-iso-propyl-1,2,3,4-tetrahydropentalene)]zirconiumdichloride,[1-(hexamethyldicyclopentafluorene-10′-yl)(5-adamantane-1-yl-1-iso-propyl-1,2,3,4-tetrahydropentalene)]zirconiumdichloride,[1-(fluorene-9′-yl)(1,5-di-tert-butyl-1,2,3,4-tetrahydropentalene)]zirconiumdichloride,[1-(2′,7′-di-tert-butylfluorene-9′-yl)(1,5-di-tert-butyl-1,2,3,4-tetrahydropentalene)]zirconiumdichloride,[1-(3′,6′-di-tert-butylfluorene-9′-yl)(1,5-di-tert-butyl-1,2,3,4-tetrahydropentalene)]zirconiumdichloride,[1-(3′,6′-di-(1-adamantyl)-fluorene-9′-yl)(1,5-di-tert-butyl-1,2,3,4-tetrahydropentalene)]zirconiumdichloride,[1-(3′,6′-di-tert-butyl-2′,7′-dimethylfluorene-9′-yl)(1,5-di-tert-butyl-1,2,3,4-tetrahydropentalene)]zirconiumdichloride,[1-(octamethylfluorene-12′-yl)(1,5-di-tert-butyl-1,2,3,4-tetrahydropentalene)]zirconiumdichloride,[1-(hexamethyldicyclopentafluorene-10′-yl)(1,5-di-tert-butyl-1,2,3,4-tetrahydropentalene)]zirconiumdichloride,[1-(fluorene-9′-yl)(5-tert-butyl-1-tert-butyl-1,2,3,4-tetrahydropentalene)]zirconiumdichloride,[1-(2′,7′-di-tert-butylfluorene-9′-yl)(5-tert-butyl-1-tert-butyl-1,2,3,4-tetrahydropentalene)]zirconiumdichloride,[1-(3′,6′-di-tert-butylfluorene-9′-yl)(5-tert-butyl-1-tert-butyl-1,2,3,4-tetrahydropentalene)]zirconiumdichloride,[1-(3′,6′-di-(1-adamantyl)-fluorene-9′-yl)(5-tert-butyl-1-tert-butyl-1,2,3,4-tetrahydropentalene)]zirconiumdichloride,[1-(3′,6′-di-tert-butyl-2′,7′-dimethylfluorene-9′-yl)(5-tert-butyl-1-tert-butyl-1,2,3,4-tetrahydropentalene)]zirconiumdichloride,[1-(octamethylfluorene-12′-yl)(5-tert-butyl-1-tert-butyl-1,2,3,4-tetrahydropentalene)]zirconiumdichloride,[1-(hexamethyldicyclopentafluorene-10′-yl)(5-tert-butyl-1-tert-butyl-1,2,3,4-tetrahydropentalene)]zirconiumdichloride,[1-(fluorene-9′-yl)(5-tert-butyl-1,3-dimethyl-1,2,3,4-tetrahydropentalene)]zirconiumdichloride,[1-(2′,7′-di-tert-butylfluorene-9′-yl)(5-tert-butyl-1,3-dimethyl-1,2,3,4-tetrahydropentalene)]zirconiumdichloride,[1-(3′,6′-di-tert-butylfluorene-9′-yl)(5-tert-butyl-1,3-dimethyl-1,2,3,4-tetrahydropentalene)]zirconiumdichloride,[1-(3′,6′-di-(1-adamantyl)-fluorene-9′-yl)(5-tert-butyl-1,3-dimethyl-1,2,3,4-tetrahydropentalene)]zirconiumdichloride,[1-(3′,6′-di-tert-butyl-2′,7′-dimethylfluorene-9′-yl)(5-tert-butyl-1,3-dimethyl-1,2,3,4-tetrahydropentalene)]zirconiumdichloride,[1-(octamethylfluorene-12′-yl)(5-tert-butyl-1,3-dimethyl-1,2,3,4-tetrahydropentalene)]zirconiumdichloride,[1-(hexamethyldicyclopentafluorene-10′-yl)(5-tert-butyl-1,3-dimethyl-1,2,3,4-tetrahydropentalene)]zirconiumdichloride,[1-(fluorene-9′-yl)(5-tert-butyl-1-iso-propyl-3-methyl-1,2,3,4-tetrahydropentalene)]zirconiumdichloride,[1-(2′,7′-di-tert-butylfluorene-9′-yl)(5-tert-butyl-1-iso-propyl-3-methyl-1,2,3,4-tetrahydropentalene)]zirconiumdichloride,[1-(3′,6′-di-tert-butylfluorene-9′-yl)(5-tert-butyl-1-iso-propyl-3-methyl-1,2,3,4-tetrahydropentalene)]zirconiumdichloride,[1-(3′,6′-di-(1-adamantyl)-fluorene-9′-yl)(5-tert-butyl-1-iso-propyl-3-methyl-1,2,3,4-tetrahydropentalene)]zirconiumdichloride,[1-(3′,6′-di-tert-butyl-2′,7′-dimethylfluorene-9′-yl)(5-tert-butyl-1-iso-propyl-3-methyl-1,2,3,4-tetrahydropentalene)]zirconiumdichloride, [1-(octamethylfluorene-12′-yl)(5-tert-butyl-1-iso-propyl-3-methyl-1,2,3,4-tetrahydropentalene)]zirconiumdichloride,[1-(hexamethyldicyclopentafluorene-10′-yl)(5-tert-butyl-1-iso-propyl-3-methyl-1,2,3,4-tetrahydropentalene)]zirconiumdichloride,[1-(fluorene-9′-yl)(1,5-di-tert-butyl-3-methyl-1,2,3,4-tetrahydropentalene)]zirconiumdichloride,[1-(2′,7′-di-tert-butylfluorene-9′-yl)(1,5-di-tert-butyl-3-methyl-1,2,3,4-tetrahydropentalene)]zirconiumdichloride,[1-(3′,6′-di-tert-butylfluorene-9′-yl)(1,5-di-tert-butyl-3-methyl-1,2,3,4-tetrahydropentalene)]zirconiumdichloride,[1-(3′,6′-di-(1-adamantyl)-fluorene-9′-yl)(1,5-di-tert-butyl-3-methyl-1,2,3,4-tetrahydropentalene)]zirconiumdichloride,[1-(3′,6′-di-tert-butyl-2′,7′-dimethylfluorene-9′-yl)(1,5-di-tert-butyl-3-methyl-1,2,3,4-tetrahydropentalene)]zirconiumdichloride,[1-(octamethylfluorene-12′-yl)(1,5-di-tert-butyl-3-methyl-1,2,3,4-tetrahydropentalene)]zirconiumdichloride,[1-(hexamethyldicyclopentafluorene-10′-yl)(1,5-di-tert-butyl-3-methyl-1,2,3,4-tetrahydropentalene)]zirconiumdichloride,[1-(fluorene-9′-yl)(5-tert-butyl-1-methyl-3-iso-propyl-1,2,3,4-tetrahydropentalene)]zirconiumdichloride,[1-(2′,7′-di-tert-butylfluorene-9′-yl)(5-tert-butyl-1-methyl-3-iso-propyl-1,2,3,4-tetrahydropentalene)]zirconiumdichloride,[1-(3′,6′-di-tert-butylfluorene-9′-yl)(5-tert-butyl-1-methyl-3-iso-propyl-1,2,3,4-tetrahydropentalene)]zirconiumdichloride,[1-(3′,6′-di-(1-adamantyl)-fluorene-9′-yl)(5-tert-butyl-1-methyl-3-iso-propyl-1,2,3,4-tetrahydropentalene)]zirconiumdichloride, [1-(3′,6′-di-tert-butyl-2′,7′-dimethylfluorene-9′-yl)(5-tert-butyl-1-methyl-3-iso-propyl-1,2,3,4-tetrahydropentalene)]zirconiumdichloride, [1-(octamethylfluorene-12′-yl)(5-tert-butyl-1-methyl-3-iso-propyl-1,2,3,4-tetrahydropentalene)]zirconiumdichloride,[1-(hexamethyldicyclopentafluorene-10′-yl)(5-tert-butyl-1-methyl-3-iso-propyl-1,2,3,4-tetrahydropentalene)]zirconiumdichloride, [1-(fluorene-9′-yl)(5-adamantane-1-yl-1,3-di-iso-propyl-1,2,3,4-tetrahydropentalene)]zirconiumdichloride,[1-(2′,7′-di-tert-butylfluorene-9′-yl)(5-adamantane-1-yl-1,3-di-iso-propyl-1,2,3,4-tetrahydropentalene)]zirconiumdichloride,[1-(3′,6′-di-tert-butylfluorene-9′-yl)(5-adamantane-1-yl-1,3-di-iso-propyl-1,2,3,4-tetrahydropentalene)]zirconiumdichloride,[1-(3′,6′-di-(1-adamantyl)-fluorene-9′-yl)(5-adamantane-1-yl-1,3-di-iso-propyl-1,2,3,4-tetrahydropentalene)]zirconiumdichloride,[1-(3′,6′-di-tert-butyl-2′,7′-dimethylfluorene-9′-yl)(5-adamantane-1-yl-1,3-di-iso-propyl-1,2,3,4-tetrahydropentalene)]zirconiumdichloride,[1-(octamethylfluorene-12′-yl)(5-adamantane-1-yl-1,3-di-iso-propyl-1,2,3,4-tetrahydropentalene)]zirconiumdichloride,[1-(hexamethyldicyclopentafluorene-10′-yl)(5-adamantane-1-yl-1,3-di-iso-propyl-1,2,3,4-tetrahydropentalene)]zirconiumdichloride,[1-(fluorene-9′-yl)(5-tert-butyl-1-ethyl-3-iso-propyl-1,2,3,4-tetrahydropentalene)]zirconiumdichloride,[1-(2′,7′-di-tert-butylfluorene-9′-yl)(5-tert-butyl-1-ethyl-3-iso-propyl-1,2,3,4-tetrahydropentalene)]zirconiumdichloride,[1-(3′,6′-di-tert-butylfluorene-9′-yl)(5-tert-butyl-1-ethyl-3-iso-propyl-1,2,3,4-tetrahydropentalene)]zirconiumdichloride,[1-(3′,6′-di-(1-adamantyl)-fluorene-9′-yl)(5-tert-butyl-1-ethyl-3-iso-propyl-1,2,3,4-tetrahydropentalene)]zirconiumdichloride,[1-(3′,6′-di-tert-butyl-2′,7′-dimethylfluorene-9′-yl)(5-tert-butyl-1-ethyl-3-iso-propyl-1,2,3,4-tetrahydropentalene)]zirconiumdichloride, [1-(octamethylfluorene-12′-yl)(5-tert-butyl-1-ethyl-3-iso-propyl-1,2,3,4-tetrahydropentalene)]zirconiumdichloride,[1-(hexamethyldicyclopentafluorene-10′-yl)(5-tert-butyl-1-ethyl-3-iso-propyl-1,2,3,4-tetrahydropentalene)]zirconiumdichloride,[1-(fluorene-9′-yl)(5-tert-butyl-1,3-di-iso-propyl-1,2,3,4-tetrahydropentalene)]zirconiumdichloride,[1-(2′,7′-di-tert-butylfluorene-9′-yl)(5-tert-butyl-1,3-di-iso-propyl-1,2,3,4-tetrahydropentalene)]zirconiumdichloride,[1-(3′,6′-di-tert-butylfluorene-9′-yl)(5-tert-butyl-1,3-di-iso-propyl-1,2,3,4-tetrahydropentalene)]zirconiumdichloride,[1-(3′,6′-di-(1-adamantyl)-fluorene-9′-yl)(5-tert-butyl-1,3-di-iso-propyl-1,2,3,4-tetrahydropentalene)]zirconiumdichloride,[1-(3′,6′-di-tert-butyl-2′,7′-dimethylfluorene-9′-yl)(5-tert-butyl-1,3-di-iso-propyl-1,2,3,4-tetrahydropentalene)]zirconiumdichloride,[1-(octamethylfluorene-12′-yl)(5-tert-butyl-1,3-di-iso-propyl-1,2,3,4-tetrahydropentalene)]zirconiumdichloride,[1-(hexamethyldicyclopentafluorene-10′-yl)(5-tert-butyl-1,3-di-iso-propyl-1,2,3,4-tetrahydropentalene)]zirconiumdichloride,[1-(fluorene-9′-yl)(1,5-di-tert-butyl-3-iso-propyl-1,2,3,4-tetrahydropentalene)]zirconiumdichloride,[1-(2′,7′-di-tert-butylfluorene-9′-yl)(1,5-di-tert-butyl-3-iso-propyl-1,2,3,4-tetrahydropentalene)]zirconiumdichloride,[1-(3′,6′-di-tert-butylfluorene-9′-yl)(1,5-di-tert-butyl-3-iso-propyl-1,2,3,4-tetrahydropentalene)]zirconiumdichloride,[1-(3′,6′-di-(1-adamantyl)-fluorene-9′-yl)(1,5-di-tert-butyl-3-iso-propyl-1,2,3,4-tetrahydropentalene)]zirconiumdichloride,[1-(3′,6′-di-tert-butyl-2′,7′-dimethylfluorene-9′-yl)(1,5-di-tert-butyl-3-iso-propyl-1,2,3,4-tetrahydropentalene)]zirconiumdichloride,[1-(octamethylfluorene-12′-yl)(1,5-di-tert-butyl-3-iso-propyl-1,2,3,4-tetrahydropentalene)]zirconiumdichloride,[1-(hexamethyldicyclopentafluorene-10′-yl)(1,5-di-tert-butyl-3-iso-propyl-1,2,3,4-tetrahydropentalene)]zirconiumdichloride,[1-(fluorene-9′-yl)(3,5-tert-butyl-1-methyl-1,2,3,4-tetrahydropentalene)]zirconiumdichloride,[1-(2′,7′-di-tert-butylfluorene-9′-yl)(3,5-tert-butyl-1-methyl-1,2,3,4-tetrahydropentalene)]zirconiumdichloride,[1-(3′,6′-di-tert-butylfluorene-9′-yl)(3,5-tert-butyl-1-methyl-1,2,3,4-tetrahydropentalene)]zirconiumdichloride,[1-(3′,6′-di-(1-adamantyl)-fluorene-9′-yl)(3,5-tert-butyl-1-methyl-1,2,3,4-tetrahydropentalene)]zirconiumdichloride,[1-(3′,6′-di-tert-butyl-2′,7′-dimethylfluorene-9′-yl)(3,5-tert-butyl-1-methyl-1,2,3,4-tetrahydropentalene)]zirconiumdichloride,[1-(octamethylfluorene-12′-yl)(3,5-tert-butyl-1-methyl-1,2,3,4-tetrahydropentalene)]zirconiumdichloride,[1-(hexamethyldicyclopentafluorene-10′-yl)(3,5-tert-butyl-1-methyl-1,2,3,4-tetrahydropentalene)]zirconiumdichloride,[1-(fluorene-9′-yl)(5-adamantane-1-yl-1-iso-propyl-3-tert-butyl-1,2,3,4-tetrahydropentalene)]zirconiumdichloride,[1-(2′,7′-di-tert-butylfluorene-9′-yl)(5-adamantane-1-yl-1-iso-propyl-3-tert-butyl-1,2,3,4-tetrahydropentalene)]zirconiumdichloride,[1-(3′,6′-di-tert-butylfluorene-9′-yl)(5-adamantane-1-yl-1-iso-propyl-3-tert-butyl-1,2,3,4-tetrahydropentalene)]zirconiumdichloride,[1-(3′,6′-di-(1-adamantyl)-fluorene-9′-yl)(5-adamantane-1-yl-1-iso-propyl-3-tert-butyl-1,2,3,4-tetrahydropentalene)]zirconiumdichloride,[1-(3′,6′-di-tert-butyl-2′,7′-dimethylfluorene-9′-yl)(5-adamantane-1-yl-1-iso-propyl-3-tert-butyl-1,2,3,4-tetrahydropentalene)]zirconiumdichloride,[1-(octamethylfluorene-12′-yl)(5-adamantane-1-yl-1-iso-propyl-3-tert-butyl-1,2,3,4-tetrahydropentalene)]zirconiumdichloride,[1-(hexamethyldicyclopentafluorene-10′-yl)(5-adamantane-1-yl-1-iso-propyl-3-tert-butyl-1,2,3,4-tetrahydropentalene)]zirconiumdichloride,[1-(fluorene-9′-yl)(3,5-tert-butyl-1-ethyl-1,2,3,4-tetrahydropentalene)]zirconiumdichloride,[1-(2′,7′-di-tert-butylfluorene-9′-yl)(3,5-tert-butyl-1-ethyl-1,2,3,4-tetrahydropentalene)]zirconiumdichloride,[1-(3′,6′-di-tert-butylfluorene-9′-yl)(3,5-tert-butyl-1-ethyl-1,2,3,4-tetrahydropentalene)]zirconiumdichloride,[1-(3′,6′-di-(1-adamantyl)-fluorene-9′-yl)(3,5-tert-butyl-1-ethyl-1,2,3,4-tetrahydropentalene)]zirconiumdichloride,[1-(3′,6′-di-tert-butyl-2′,7′-dimethylfluorene-9′-yl)(3,5-tert-butyl-1-ethyl-1,2,3,4-tetrahydropentalene)]zirconiumdichloride,[1-(octamethylfluorene-12′-yl)(3,5-tert-butyl-1-ethyl-1,2,3,4-tetrahydropentalene)]zirconiumdichloride,[1-(hexamethyldicyclopentafluorene-10′-yl)(3,5-tert-butyl-1-ethyl-1,2,3,4-tetrahydropentalene)]zirconiumdichloride,[1-(fluorene-9′-yl)(3,5-tert-butyl-1-iso-propyl-1,2,3,4-tetrahydropentalene)]zirconiumdichloride,[1-(2′,7′-di-tert-butylfluorene-9′-yl)(3,5-tert-butyl-1-iso-propyl-1,2,3,4-tetrahydropentalene)]zirconiumdichloride,[1-(3′,6′-di-tert-butylfluorene-9′-yl)(3,5-tert-butyl-1-iso-propyl-1,2,3,4-tetrahydropentalene)]zirconiumdichloride,[1-(3′,6′-di-(1-adamantyl)-fluorene-9′-yl)(3,5-tert-butyl-1-iso-propyl-1,2,3,4-tetrahydropentalene)]zirconiumdichloride,[1-(3′,6′-di-tert-butyl-2′,7′-dimethylfluorene-9′-yl)(3,5-tert-butyl-1-iso-propyl-1,2,3,4-tetrahydropentalene)]zirconiumdichloride,[1-(octamethylfluorene-12′-yl)(3,5-tert-butyl-1-iso-propyl-1,2,3,4-tetrahydropentalene)]zirconiumdichloride,[1-(hexamethyldicyclopentafluorene-10′-yl)(3,5-tert-butyl-1-iso-propyl-1,2,3,4-tetrahydropentalene)]zirconiumdichloride,[1-(fluorene-9′-yl)(5-tert-butyl-1-methyl-3-cylohexyl-1,2,3,4-tetrahydropentalene)]zirconiumdichloride,[1-(2′,7′-di-tert-butylfluorene-9′-yl)(5-tert-butyl-1-methyl-3-cylohexyl-1,2,3,4-tetrahydropentalene)]zirconiumdichloride,[1-(3′,6′-di-tert-butylfluorene-9′-yl)(5-tert-butyl-1-methyl-3-cylohexyl-1,2,3,4-tetrahydropentalene)]zirconiumdichloride,[1-(3′,6′-di-(1-adamantyl)-fluorene-9′-yl)(5-tert-butyl-1-methyl-3-cylohexyl-1,2,3,4-tetrahydropentalene)]zirconiumdichloride,[1-(3′,6′-di-tert-butyl-2′,7′-dimethylfluorene-9′-yl)(5-tert-butyl-1-methyl-3-cylohexyl-1,2,3,4-tetrahydropentalene)]zirconiumdichloride, [1-(octamethylfluorene-12′-yl)(5-tert-butyl-1-methyl-3-cylohexyl-1,2,3,4-tetrahydropentalene)]zirconiumdichloride,[1-(hexamethyldicyclopentafluorene-10′-yl)(5-tert-butyl-1-methyl-3-cylohexyl-1,2,3,4-tetrahydropentalene)]zirconiumdichloride,[1-(fluorene-9′-yl)(5-adamantane-1-yl-1-iso-propyl-3-cylohexyl-1,2,3,4-tetrahydropentalene)]zirconiumdichloride,[1-(2′,7′-di-tert-butylfluorene-9′-yl)(5-adamantane-1-yl-1-iso-propyl-3-cylohexyl-1,2,3,4-tetrahydropentalene)]zirconiumdichloride,[1-(3′,6′-di-tert-butylfluorene-9′-yl)(5-adamantane-1-yl-1-iso-propyl-3-cylohexyl-1,2,3,4-tetrahydropentalene)]zirconiumdichloride,[1-(3′,6′-di-(1-adamantyl)-fluorene-9′-yl)(5-adamantane-1-yl-1-iso-propyl-3-cylohexyl-1,2,3,4-tetrahydropentalene)]zirconiumdichloride,[1-(3′,6′-di-tert-butyl-2′,7′-dimethylfluorene-9′-yl)(5-adamantane-1-yl-1-iso-propyl-3-cylohexyl-1,2,3,4-tetrahydropentalene)]zirconiumdichloride,[1-(octamethylfluorene-12′-yl)(5-adamantane-1-yl-1-iso-propyl-3-cylohexyl-1,2,3,4-tetrahydropentalene)]zirconiumdichloride,[1-(hexamethyldicyclopentafluorene-10′-yl)(5-adamantane-1-yl-1-iso-propyl-3-cylohexyl-1,2,3,4-tetrahydropentalene)]zirconiumdichloride,[1-(fluorene-9′-yl)(5-tert-butyl-1-ethyl-3-cylohexyl-1,2,3,4-tetrahydropentalene)]zirconiumdichloride,[1-(2′,7′-di-tert-butylfluorene-9′-yl)(5-tert-butyl-1-ethyl-3-cylohexyl-1,2,3,4-tetrahydropentalene)]zirconiumdichloride,[1-(3′,6′-di-tert-butylfluarene-9′-yl)(5-tert-butyl-1-ethyl-3-cylohexyl-1,2,3,4-tetrahydropentalene)]zirconiumdichloride,[1-(3′,6′-di-(1-adamantyl)-fluarene-9′-yl)(5-tert-butyl-1-ethyl-3-cylohexyl-1,2,3,4-tetrahydropentalene)]zirconiumdichloride,[1-(3′,6′-di-tert-butyl-2′,7′-dimethylfluarene-9′-yl)(5-tert-butyl-1-ethyl-3-cylohexyl-1,2,3,4-tetrahydropentalene)]zirconiumdichloride,[1-(actamethylfluarene-12′-yl)(5-tert-butyl-1-ethyl-3-cylohexyl-1,2,3,4-tetrahydropentalene)]zirconiumdichloride,[1-(hexamethyldicyclopentafluorene-10′-yl)(5-tert-butyl-1-ethyl-3-cylohexyl-1,2,3,4-tetrahydropentalene)]zirconiumdichloride,[1-(fluarene-9′-yl)(5-tert-butyl-1-iso-propyl-3-cylohexyl-1,2,3,4-tetrahydropentalene)]zirconiumdichloride,[1-(2′,7′-di-tert-butylfluarene-9′-yl)(5-tert-butyl-1-iso-propyl-3-cylohexyl-1,2,3,4-tetrahydropentalene)]zirconiumdichloride,[1-(3′,6′-di-tert-butylfluarene-9′-yl)(5-tert-butyl-1-iso-propyl-3-cylohexyl-1,2,3,4-tetrahydropentalene)]zirconiumdichloride,[1-(3′,6′-di-(1-adamantyl)-fluarene-9′-yl)(5-tert-butyl-1-iso-propyl-3-cylohexyl-1,2,3,4-tetrahydropentalene)]zirconiumdichloride,[1-(3′,6′-di-tert-butyl-2′,7′-dimethylfluorene-9′-yl)(5-tert-butyl-1-iso-propyl-3-cylohexyl-1,2,3,4-tetrahydropentalene)]zirconiumdichloride,[1-(octamethylfluorene-12′-yl)(5-tert-butyl-1-iso-propyl-3-cylohexyl-1,2,3,4-tetrahydropentalene)]zirconiumdichloride,[1-(hexamethyldicyclopentafluorene-10′-yl)(5-tert-butyl-1-iso-propyl-3-cylohexyl-1,2,3,4-tetrahydropentalene)]zirconiumdichloride,[1-(fluorene-9′-yl) (5-tert-butyl-1-methyl-3-(3-cyclohexenyl)-1,2,3,4-tetrahydropentalene)]zirconiumdichloride,[1-(2′,7′-di-tert-butylfluorene-9′-yl)(5-tert-butyl-1-methyl-3-(3-cyclohexenyl)-1,2,3,4-tetrahydropentalene)]zirconiumdichloride,[1-(3′,6′-di-tert-butylfluorene-9′-yl)(5-tert-butyl-1-methyl-3-(3-cyclohexeny))-1,2,3,4-tetrahydropentalene)]zirconiumdichloride,[1-(3′,6′-di-(1-adamantyl)-fluorene-9′-yl)(5-tert-butyl-1-methyl-3-(3-cyclohexeny))-1,2,3,4-tetrahydropentalene)]zirconiumdichloride,[1-(3′,6′-di-tert-butyl-2′,7′-dimethylfluorene-9′-yl)(5-tert-butyl-1-methyl-3-(3-cyclohexeny))-1,2,3,4-tetrahydropentalene)]zirconiumdichloride,[1-(octamethylfluorene-12′-yl)(5-tert-butyl-1-methyl-3-(3-cyclohexenyl)-1,2,3,4-tetrahydropentalene)]zirconiumdichloride,[1-(hexamethyldicyclopentafluorene-10′-yl)(5-tert-butyl-1-methyl-3-(3-cyclohexenyl)-1,2,3,4-tetrahydropentalene)]zirconiumdichloride,[1-(fluorene-9′-yl)(5-adamantane-1-yl-1-iso-propyl-3-(3-cyclohexenyl)-1,2,3,4-tetrahydropentalene)]zirconiumdichloride,[1-(2′,7′-di-tert-butylfluorene-9′-yl)(5-adamantane-1-yl-1-iso-propyl-3-(3-cyclohexenyl)-1,2,3,4-tetrahydropentalene)]zirconiumdichloride, [1-(3′,6′-di-tert-butylfluorene-9′-yl)(5-adamantane-1-yl-1-iso-propyl-3-(3-cyclohexenyl)-1,2,3,4-tetrahydropentalene)]zirconiumdichloride, [1-(3′,6′-di-(1-adamantyl)-fluorene-9′-yl)(5-adamantane-1-yl-1-iso-propyl-3-(3-cyclohexenyl)-1,2,3,4-tetrahydropentalene)]zirconiumdichloride,[1-(3′,6′-di-tert-butyl-2′,7′-dimethylfluorene-9′-yl)(5-adamantane-1-yl-1-iso-propyl-3-(3-cyclohexenyl)-1,2,3,4-tetrahydropentalene)]zirconiumdichloride,[1-(octamethylfluorene-12′-yl)(5-adamantane-1-yl-1-iso-propyl-3-(3-cyclohexenyl)-1,2,3,4-tetrahydropentalene)]zirconiumdichloride,[1-(hexamethyldicyclopentafluorene-10′-yl)(5-adamantane-1-yl-1-iso-propyl-3-(3-cyclohexenyl)-1,2,3,4-tetrahydropentalene)]zirconiumdichloride,[1-(fluorene-9′-yl)(5-tert-butyl-1-ethyl-3-(3-cyclohexenyl)-1,2,3,4-tetrahydropentalene)]zirconiumdichloride,[1-(2′,7′-di-tert-butylfluorene-9′-yl)(5-tert-butyl-1-ethyl-3-(3-cyclohexenyl)-1,2,3,4-tetrahydropentalene)]zirconiumdichloride,[1-(3′,6′-di-tert-butylfluorene-9′-yl)(5-tert-butyl-1-ethyl-3-(3-cyclohexenyl)-1,2,3,4-tetrahydropentalene)]zirconiumdichloride,[1-(3′,6′-di-(1-adamantyl)-fluorene-9′-yl)(5-tert-butyl-1-ethyl-3-(3-cyclohexenyl)-1,2,3,4-tetrahydropentalene)]zirconiumdichloride,[1-(3′,6′-di-tert-butyl-2′,7′-dimethylfluorene-9′-yl)(5-tert-butyl-1-ethyl-3-(3-cyclohexenyl)-1,2,3,4-tetrahydropentalene)]zirconiumdichloride,[1-(octamethylfluorene-12′-yl)(5-tert-butyl-1-ethyl-3-(3-cyclohexenyl)-1,2,3,4-tetrahydropentalene)]zirconiumdichloride,[1-(hexamethyldicyclopentafluorene-10′-yl)(5-tert-butyl-1-ethyl-3-(3-cyclohexenyl)-1,2,3,4-tetrahydropentalene)]zirconiumdichloride,[1-(fluorene-9′-yl)(5-tert-butyl-1-iso-propyl-3-(3-cyclohexenyl)-1,2,3,4-tetrahydropentalene)]zirconiumdichloride,[1-(2′,7′-di-tert-butylfluorene-9′-yl)(5-tert-butyl-1-iso-propyl-3-(3-cyclohexenyl)-1,2,3,4-tetrahydropentalene)]zirconiumdichloride,[1-(3′,6′-di-tert-butylfluorene-9′-yl)(5-tert-butyl-1-iso-propyl-3-(3-cyclohexenyl)-1,2,3,4-tetrahydropentalene)]zirconiumdichloride,[1-(3′,6′-di-(1-adamantyl)-fluorene-9′-yl)(5-tert-butyl-1-iso-propyl-3-(3-cyclohexenyl)-1,2,3,4-tetrahydropentalene)]zirconiumdichloride,[1-(3′,6′-di-tert-butyl-2′,7′-dimethylfluorene-9′-yl)(5-tert-butyl-1-iso-propyl-3-(3-cyclohexenyl)-1,2,3,4-tetrahydropentalene)]zirconiumdichloride,[1-(octamethylfluorene-12′-yl)(5-tert-butyl-1-iso-propyl-3-(3-cyclohexenyl)-1,2,3,4-tetrahydropentalene)]zirconiumdichloride,[1-(hexamethyldicyclopentafluorene-10′-yl)(5-tert-butyl-1-iso-propyl-3-(3-cyclohexenyl)-1,2,3,4-tetrahydropentalene)]zirconiumdichloride, [1-(fluorene-9′-yl)(5-tert-butyl-1-methyl-3-(bicyclo[2.2.1]hepta-5-ene-2-yl)-1,2,3,4-tetrahydropentalene)]zirconiumdichloride,[1-(2′,7′-di-tert-butylfluorene-9′-yl)(5-tert-butyl-1-methyl-3-(bicyclo[2.2.1]hepta-5-ene-2-yl)-1,2,3,4-tetrahydropentalene)]zirconiumdichloride,[1-(3′,6′-di-tert-butylfluorene-9′-yl)(5-tert-butyl-1-methyl-3-(bicyclo[2.2.1]hepta-5-ene-2-yl)-1,2,3,4-tetrahydropentalene)]zirconiumdichloride,[1-(3′,6′-di-(1-adamantyl)-fluorene-9′-yl)(5-tert-butyl-1-methyl-3-(bicyclo[2.2.1]hepta-5-ene-2-yl)-1,2,3,4-tetrahydropentalene)]zirconiumdichloride,[1-(3′,6′-di-tert-butyl-2′,7′-dimethylfluorene-9′-yl)(5-tert-butyl-1-methyl-3-(bicyclo[2.2.1]hepta-5-ene-2-yl)-1,2,3,4-tetrahydropentalene)]zirconiumdichloride,[1-(octamethylfluorene-12′-yl)(5-tert-butyl-1-methyl-3-(bicyclo[2.2.1]hepta-5-ene-2-yl)-1,2,3,4-tetrahydropentalene)]zirconiumdichloride, [1-(hexamethyldicyclopentafluorene-10′-yl)(5-tert-butyl-1-methyl-3-(bicyclo[2.2.1]hepta-5-ene-2-yl)-1,2,3,4-tetrahydropentalene)]zirconiumdichloride,[1-(fluorene-9′-yl)(5-adamantane-1-yl-1-iso-propyl-3-(bicyclo[2.2.1]hepta-5-ene-2-yl)-1,2,3,4-tetrahydropentalene)]zirconiumdichloride,[1-(2′,7′-di-tert-butylfluorene-9′-yl)(5-adamantane-1-yl-1-iso-propyl-3-(bicyclo[2.2.1]hepta-5-ene-2-yl)-1,2,3,4-tetrahydropentalene)]zirconiumdichloride,[1-(3′,6′-di-tert-butylfluorene-9′-yl)(5-adamantane-1-yl-1-iso-propyl-3-(bicyclo[2.2.1]hepta-5-ene-2-yl)-1,2,3,4-tetrahydropentalene)]zirconiumdichloride,[1-(3′,6′-di-(1-adamantyl)-fluorene-9′-yl)(5-adamantane-1-yl-1-iso-propyl-3-(bicyclo[2.2.1]hepta-5-ene-2-yl)-1,2,3,4-tetrahydropentalene)]zirconiumdichloride,[1-(3′,6′-di-tert-butyl-2′,7′-dimethylfluorene-9′-yl)(5-adamantane-1-yl-1-iso-propyl-3-(bicyclo[2.2.1]hepta-5-ene-2-yl)-1,2,3,4-tetrahydropentalene)]zirconiumdichloride,[1-(octamethylfluorene-12′-yl)(5-adamantane-1-yl-1-iso-propyl-3-(bicyclo[2.2.1]hepta-5-ene-2-yl)-1,2,3,4-tetrahydropentalene)]zirconiumdichloride,[1-(hexamethyldicyclopentafluorene-10′-yl)(5-adamantane-1-yl-1-iso-propyl-3-(bicyclo[2.2.1]hepta-5-ene-2-yl)-1,2,3,4-tetrahydropentalene)]zirconiumdichloride,[1-(fluorene-9′-yl)(5-tert-butyl-1-iso-propyl-3-(bicyclo[2.2.1]hepta-5-ene-2-yl)-1,2,3,4-tetrahydropentalene)]zirconiumdichloride,[1-(2′,7′-di-tert-butylfluorene-9′-yl)(5-tert-butyl-1-iso-propyl-3-(bicyclo[2.2.1]hepta-5-ene-2-yl)-1,2,3,4-tetrahydropentalene)]zirconiumdichloride,[1-(3′,6′-di-tert-butylfluorene-9′-yl)(5-tert-butyl-1-iso-propyl-3-(bicyclo[2.2.1]hepta-5-ene-2-yl)-1,2,3,4-tetrahydropentalene)]zirconiumdichloride,[1-(3′,6′-di-(1-adamantyl)-fluorene-9′-yl)(5-tert-butyl-1-iso-propyl-3-(bicyclo[2.2.1]hepta-5-ene-2-yl)-1,2,3,4-tetrahydropentalene)]zirconiumdichloride,[1-(3′,6′-di-tert-butyl-2′,7′-dimethylfluorene-9′-yl)(5-tert-butyl-1-iso-propyl-3-(bicyclo[2.2.1]hepta-5-ene-2-yl)-1,2,3,4-tetrahydropentalene)]zirconiumdichloride,[1-(octamethylfluorene-12′-yl)(5-tert-butyl-1-iso-propyl-3-(bicyclo[2.2.1]hepta-5-ene-2-yl)-1,2,3,4-tetrahydropentalene)]zirconiumdichloride,[1-(hexamethyldicyclopentafluorene-10′-yl)(5-tert-butyl-1-iso-propyl-3-(bicyclo[2.2.1]hepta-5-ene-2-yl)-1,2,3,4-tetrahydropentalene)]zirconiumdichloride,[8-(fluorene-9′-yl)(3,3b,4,5,6,7,7a,8-octahydrocyclopenta[a]indene)]zirconiumdichloride,[8-(2′,7′-di-tert-butylfluorene-9′-yl)(3,3b,4,5,6,7,7a,8-octahydrocyclopenta[a]indene)]zirconiumdichloride,[8-(3′,6′-di-tert-butylfluorene-9′-yl)(3,3b,4,5,6,7,7a,8-octahydrocyclopenta[a]indene)]zirconiumdichloride,[8-(3′,6′-di-(1-adamantyl)-fluorene-9′-yl)(3,3b,4,5,6,7,7a,8-octahydrocyclopenta[a]indene)]zirconiumdichloride,[8-(3′,6′-di-tert-butyl-2′,7′-dimethylfluorene-9′-yl)(3,3b,4,5,6,7,7a,8-octahydrocyclopenta[a]indene)]zirconiumdichloride,[8-(octamethylfluorene-12′-yl)(3,3b,4,5,6,7,7a,8-octahydrocyclopenta[a]indene)]zirconiumdichloride,[8-(hexamethyldicyclopentafluorene-10′-yl)(3,3b,4,5,6,7,7a,8-octahydrocyclopenta[a]indene)]zirconiumdichloride,[8-(fluorene-9′-yl) (2-tert-butyl-8-methyl-3,3b,4,5,6,7,7a,8-octahydrocyclopenta[a]indene)]zirconiumdichloride,[8-(2′,7′-di-tert-butylfluorene-9′-yl)(2-tert-butyl-8-methyl-3,3b,4,5,6,7,7a,8-octahydrocyclopenta[a]indene)]zirconiumdichloride,[8-(3′,6′-di-tert-butylfluorene-9′-yl)(2-tert-butyl-8-methyl-3,3b,4,5,6,7,7a,8-octahydrocyclopenta[a]indene)]zirconiumdichloride,[8-(3′,6′-di-(1-adamantyl)-fluorene-9′-yl)(2-tert-butyl-8-methyl-3,3b,4,5,6,7,7a,8-octahydrocyclopenta[a]indene)]zirconiumdichloride,[8-(3′,6′-di-tert-butyl-2′,7′-dimethylfluorene-9′-yl)(2-tert-butyl-8-methyl-3,3b,4,5,6,7,7a,8-octahydrocyclopenta[a]indene)]zirconiumdichloride,[8-(octamethylfluorene-12′-yl) (2-tert-butyl-8-methyl-3,3b,4,5,6,7,7a,8-octahydrocyclopenta[a]indene)]zirconiumdichloride,[8-(hexamethyldicyclopentafluorene-10′-yl)(2-tert-butyl-8-methyl-3,3b,4,5,6,7,7a,8-octahydrocyclopenta[a]indene)]zirconiumdichloride,[8-(fluorene-9′-yl)(2-tert-butyl-8-iso-propyl-3,3b,4,5,6,7,7a,8-octahydrocyclopenta[a]indene)]zirconiumdichloride,[8-(2′,7′-di-tert-butylfluorene-9′-yl)(2-tert-butyl-8-iso-propyl-3,3b,4,5,6,7,7a,8-octahydrocyclopenta[a]indene)]zirconiumdichloride,[8-(3′,6′-di-tert-butylfluorene-9′-yl)(2-tert-butyl-8-iso-propyl-3,3b,4,5,6,7,7a,8-octahydrocyclopenta[a]indene)]zirconiumdichloride,[8-(3′,6′-di-(1-adamantyl)-fluorene-9′-yl)(2-tert-butyl-8-iso-propyl-3,3b,4,5,6,7,7a,8-octahydrocyclopenta[a]indene)]zirconiumdichloride,[8-(3′,6′-di-tert-butyl-2′,7′-dimethylfluorene-9′-yl)(2-tert-butyl-8-iso-propyl-3,3b,4,5,6,7,7a,8-octahydrocyclopenta[a]indene)]zirconiumdichloride,[8-(octamethylfluorene-12′-yl)(2-tert-butyl-8-iso-propyl-3,3b,4,5,6,7,7a,8-octahydrocyclopenta[a]indene)]zirconiumdichloride,[8-(hexamethyldicyclopentafluorene-10′-yl)(2-tert-butyl-8-iso-propyl-3,3b,4,5,6,7,7a,8-octahydrocyclopenta[a]indene)]zirconiumdichloride, [8-(fluorene-9′-yl)(2-tert-butyl-8-phenyl-3,3b,4,5,6,7,7a,8-octahydrocyclopenta[a]indene)]zirconiumdichloride,[8-(2′,7′-di-tert-butylfluorene-9′-yl)(2-tert-butyl-8-phenyl-3,3b,4,5,6,7,7a,8-octahydrocyclopenta[a]indene)]zirconiumdichloride,[8-(3′,6′-di-tert-butylfluorene-9′-yl)(2-tert-butyl-8-phenyl-3,3b,4,5,6,7,7a,8-octahydrocyclopenta[a]indene)]zirconiumdichloride,[8-(3′,6′-di-(1-adamantyl)-fluorene-9′-yl)(2-tert-butyl-8-phenyl-3,3b,4,5,6,7,7a,8-octahydrocyclopenta[a]indene)]zirconiumdichloride,[8-(3′,6′-di-tert-butyl-2′,7′-dimethylfluorene-9′-yl)(2-tert-butyl-8-phenyl-3,3b,4,5,6,7,7a,8-octahydrocyclopenta[a]indene)]zirconiumdichloride,[8-(octamethylfluorene-12′-yl) (2-tert-butyl-8-phenyl-3,3b,4,5,6,7,7a,8-octahydrocyclopenta[a]indene)]zirconiumdichloride,[8-(hexamethyldicyclopentafluorene-10′-yl)(2-tert-butyl-8-phenyl-3,3b,4,5,6,7,7a,8-octahydrocyclopenta[a]indene)]zirconiumdichloride,[8-(fluorene-9′-yl)(2-tert-butyl-5,8-dimethyl-3,3b,4,5,6,7,7a,8-octahydrocyclopenta[a]indene)]zirconiumdichloride,[8-(2′,7′-di-tert-butylfluorene-9′-yl)(2-tert-butyl-5,8-dimethyl-3,3b,4,5,6,7,7a,8-octahydrocyclopenta[a]indene)]zirconiumdichloride,[8-(3′,6′-di-tert-butylfluorene-9′-yl)(2-tert-butyl-5,8-dimethyl-3,3b,4,5,6,7,7a,8-octahydrocyclopenta[a]indene)]zirconiumdichloride,[8-(3′,6′-di-(1-adamantyl)-fluorene-9′-yl)(2-tert-butyl-5,8-dimethyl-3,3b,4,5,6,7,7a,8-octahydrocyclopenta[a]indene)]zirconiumdichloride,[8-(3′,6′-di-tert-butyl-2′,7′-dimethylfluorene-9′-yl)(2-tert-butyl-5,8-dimethyl-3,3b,4,5,6,7,7a,8-octahydrocyclopenta[a]indene)]zirconiumdichloride,[8-(octamethylfluorene-12′-yl)(2-tert-butyl-5,8-dimethyl-3,3b,4,5,6,7,7a,8-octahydrocyclopenta[a]indene)]zirconiumdichloride,[8-(hexamethyldicyclopentafluorene-10′-yl)(2-tert-butyl-5,8-dimethyl-3,3b,4,5,6,7,7a,8-octahydrocyclopenta[a]indene)]zirconiumdichloride, [8-(fluorene-9′-yl)(2-tert-butyl-8-(3-cyclohexenyl)-3,3b,4,5,6,7,7a,8-octahydrocyclopenta[a]indene)]zirconiumdichloride,[8-(2′,7′-di-tert-butylfluorene-9′-yl)(2-tert-butyl-8-(3-cyclohexenyl)-3,3b,4,5,6,7,7a,8-octahydrocyclopenta[a]indene)]zirconiumdichloride,[8-(3′,6′-di-tert-butylfluorene-9′-yl)(2-tert-butyl-8-(3-cyclohexenyl)-3,3b,4,5,6,7,7a,8-octahydrocyclopenta[a]indene)]zirconiumdichloride,[8-(3′,6′-di-(1-adamantyl)-fluorene-9′-yl)(2-tert-butyl-8-(3-cyclohexenyl)-3,3b,4,5,6,7,7a,8-octahydrocyclopenta[a]indene)]zirconiumdichloride,[8-(3′,6′-di-tert-butyl-2′,7′-dimethylfluorene-9′-yl)(2-tert-butyl-8-(3-cyclohexenyl)-3,3b,4,5,6,7,7a,8-octahydrocyclopenta[a]indene)]zirconiumdichloride,[8-(octamethylfluorene-12′-yl)(2-tert-butyl-8-(3-cyclohexenyl)-3,3b,4,5,6,7,7a,8-octahydrocyclopenta[a]indene)]zirconiumdichloride,[8-(hexamethyldicyclopentafluorene-10′-yl)(2-tert-butyl-8-(3-cyclohexenyl)-3,3b,4,5,6,7,7a,8-octahydrocyclopenta[a]indene)]zirconiumdichloride,[8-(fluorene-9′-yl)(2-(1-adamantyl)-8-methyl-3,3b,4,5,6,7,7a,8-octahydrocyclopenta[a]indene)]zirconiumdichloride,[8-(2′,7′-di-tert-butylfluorene-9′-yl)(2-(1-adamantyl)-8-methyl-3,3b,4,5,6,7,7a,8-octahydrocyclopenta[a]indene)]zirconiumdichloride,[8-(3′,6′-di-tert-butylfluorene-9′-yl)(2-(1-adamantyl)-8-methyl-3,3b,4,5,6,7,7a,8-octahydrocyclopenta[a]indene)]zirconiumdichloride,[8-(3′,6′-di-(1-adamantyl)-fluorene-9′-yl)(2-(1-adamantyl)-8-methyl-3,3b,4,5,6,7,7a,8-octahydrocyclopenta[a]indene)]zirconiumdichloride,[8-(3′,6′-di-tert-butyl-2′,7′-dimethylfluorene-9′-yl)(2-(1-adamantyl)-8-methyl-3,3b,4,5,6,7,7a,8-octahydrocyclopenta[a]indene)]zirconiumdichloride,[8-(octamethylfluorene-12′-yl)(2-(1-adamantyl)-8-methyl-3,3b,4,5,6,7,7a,8-octahydrocyclopenta[a]indene)]zirconiumdichloride,[8-(hexamethyldicyclopentafluorene-10′-yl)(2-(1-adamantyl)-8-methyl-3,3b,4,5,6,7,7a,8-octahydrocyclopenta[a]indene)]zirconiumdichloride,[8-(fluorene-9′-yl)(2-(1-adamantyl)-8-iso-propyl-3,3b,4,5,6,7,7a,8-octahydrocyclopenta[a]indene)]zirconiumdichloride,[8-(2′,7′-di-tert-butylfluorene-9′-yl)(2-(1-adamantyl)-8-iso-propyl-3,3b,4,5,6,7,7a,8-octahydrocyclopenta[a]indene)]zirconiumdichloride,[8-(3′,6′-di-tert-butylfluorene-9′-yl)(2-(1-adamantyl)-8-iso-propyl-3,3b,4,5,6,7,7a,8-octahydrocyclopenta[a]indene)]zirconiumdichloride,[8-(3′,6′-di-(1-adamantyl)-fluorene-9′-yl)(2-(1-adamantyl)-8-iso-propyl-3,3b,4,5,6,7,7a,8-octahydrocyclopenta[a]indene)]zirconiumdichloride,[8-(3′,6′-di-tert-butyl-2′,7′-dimethylfluorene-9′-yl)(2-(1-adamantyl)-8-iso-propyl-3,3b,4,5,6,7,7a,8-octahydrocyclopenta[a]indene)]zirconiumdichloride,[8-(octamethylfluorene-12′-yl)(2-(1-adamantyl)-8-iso-propyl-3,3b,4,5,6,7,7a,8-octahydrocyclopenta[a]indene)]zirconiumdichloride,[8-(hexamethyldicyclopentafluorene-10′-yl)(2-(1-adamantyl)-8-iso-propyl-3,3b,4,5,6,7,7a,8-octahydrocyclopenta[a]indene)]zirconiumdichloride,[7-(fluorene-9′-yl)(2,3,3a,4,7,7a-hexahydro-1H-cyclopenta[a]pentalene)]zirconiumdichloride,[7-(2′,7′-di-tert-butylfluorene-9′-yl)(2,3,3a,4,7,7a-hexahydro-1H-cyclopenta[a]pentalene)]zirconiumdichloride,[7-(3′,6′-di-tert-butylfluorene-9′-yl)(2,3,3a,4,7,7a-hexahydro-1H-cyclopenta[a]pentalene)]zirconiumdichloride,[7-(3′,6′-di-(1-adamantyl)-fluorene-9′-yl)(2,3,3a,4,7,7a-hexahydro-1H-cyclopenta[a]pentalene)]zirconiumdichloride,[7-(3′,6′-di-tert-butyl-2′,7′-dimethylfluorene-9′-yl)(2,3,3a,4,7,7a-hexahydro-1H-cyclopenta[a]pentalene)]zirconiumdichloride,[7-(octamethylfluorene-12′-yl)(2,3,3a,4,7,7a-hexahydro-1H-cyclopenta[a]pentalene)]zirconiumdichloride,[7-(hexamethyldicyclopentafluorene-10′-yl)(2,3,3a,4,7,7a-hexahydro-1H-cyclopenta[a]pentalene)]zirconiumdichloride,[7-(fluorene-9′-yl)(5-tert-butyl-7-methyl-2,3,3a,4,7,7a-hexahydro-1H-cyclopenta[a]pentalene)]zirconiumdichloride,[7-(2′,7′-di-tert-butylfluorene-9′-yl)(5-tert-butyl-7-methyl-2,3,3a,4,7,7a-hexahydro-1H-cyclopenta[a]pentalene)]zirconiumdichloride,[7-(3′,6′-di-tert-butylfluorene-9′-yl)(5-tert-butyl-7-methyl-2,3,3a,4,7,7a-hexahydro-1H-cyclopenta[a]pentalene)]zirconiumdichloride,[7-(3′,6′-di-(1-adamantyl)-fluorene-9′-yl)(5-tert-butyl-7-methyl-2,3,3a,4,7,7a-hexahydro-1H-cyclopenta[a]pentalene)]zirconiumdichloride,[7-(3′,6′-di-tert-butyl-2′,7′-dimethylfluorene-9′-yl)(5-tert-butyl-7-methyl-2,3,3a,4,7,7a-hexahydro-1H-cyclopenta[a]pentalene)]zirconiumdichloride,[7-(octamethylfluorene-12′-yl)(5-tert-butyl-7-methyl-2,3,3a,4,7,7a-hexahydro-1H-cyclopenta[a]pentalene)]zirconiumdichloride,[7-(hexamethyldicyclopentafluorene-10′-yl)(5-tert-butyl-7-methyl-2,3,3a,4,7,7a-hexahydro-1H-cyclopenta[a]pentalene)]zirconiumdichloride,[7-(fluorene-9′-yl)(5-tert-butyl-7-iso-propyl-2,3,3a,4,7,7a-hexahydro-1H-cyclopenta[a]pentalene)]zirconiumdichloride,[7-(2′,7′-di-tert-butylfluorene-9′-yl)(5-tert-butyl-7-iso-propyl-2,3,3a,4,7,7a-hexahydro-1H-cyclopenta[a]pentalene)]zirconiumdichloride,[7-(3′,6′-di-tert-butylfluorene-9′-yl)(5-tert-butyl-7-iso-propyl-2,3,3a,4,7,7a-hexahydro-1H-cyclopenta[a]pentalene)]zirconiumdichloride,[7-(3′,6′-di-(1-adamantyl)-fluorene-9′-yl)(5-tert-butyl-7-iso-propyl-2,3,3a,4,7,7a-hexahydro-1H-cyclopenta[a]pentalene)]zirconiumdichloride,[7-(3′,6′-di-tert-butyl-2′,7′-dimethylfluorene-9′-yl)(5-tert-butyl-7-iso-propyl-2,3,3a,4,7,7a-hexahydro-1H-cyclopenta[a]pentalene)]zirconiumdichloride,[7-(octamethylfluorene-12′-yl)(5-tert-butyl-7-iso-propyl-2,3,3a,4,7,7a-hexahydro-1H-cyclopenta[a]pentalene)]zirconiumdichloride,[7-(hexamethyldicyclopentafluorene-10′-yl)(5-tert-butyl-7-iso-propyl-2,3,3a,4,7,7a-hexahydro-1H-cyclopenta[a]pentalene)]zirconiumdichloride,[7-(fluorene-9′-yl)(2-tert-butyl-8-phenyl-2,3,3a,4,7,7a-hexahydro-1H-cyclopenta[a]pentalene)]zirconiumdichloride,[7-(2′,7′-di-tert-butylfluorene-9′-yl)(2-tert-butyl-8-phenyl-2,3,3a,4,7,7a-hexahydro-1H-cyclopenta[a]pentalene)]zirconiumdichloride,[7-(3′,6′-di-tert-butylfluorene-9′-yl)(2-tert-butyl-8-phenyl-2,3,3a,4,7,7a-hexahydro-1H-cyclopenta[a]pentalene)]zirconiumdichloride,[7-(3′,6′-di-(1-adamantyl)-fluorene-9′-yl)(2-tert-butyl-8-phenyl-2,3,3a,4,7,7a-hexahydro-1H-cyclopenta[a]pentalene)]zirconiumdichloride,[7-(3′,6′-di-tert-butyl-2′,7′-dimethylfluorene-9′-yl)(2-tert-butyl-8-phenyl-2,3,3a,4,7,7a-hexahydro-1H-cyclopenta[a]pentalene)]zirconiumdichloride,[7-(octamethylfluorene-12′-yl) (2-tert-butyl-8-phenyl-2,3,3a,4,7,7a-hexahydro-1H-cyclopenta[a]pentalene)]zirconiumdichloride,[7-(hexamethyldicyclopentafluorene-10′-yl)(2-tert-butyl-8-phenyl-2,3,3a,4,7,7a-hexahydro-1H-cyclopenta[a]pentalene)]zirconiumdichloride,[7-(fluorene-9′-yl)(5-tert-butyl-7-cylohexyl-2,3,3a,4,7,7a-hexahydro-1H-cyclopenta[a]pentalene)]zirconiumdichloride,[7-(2′,7′-di-tert-butylfluorene-9′-yl)(5-tert-butyl-7-cylohexyl-2,3,3a,4,7,7a-hexahydro-1H-cyclopenta[a]pentalene)]zirconiumdichloride,[7-(3′,6′-di-tert-butylfluorene-9′-yl)(5-tert-butyl-7-cylohexyl-2,3,3a,4,7,7a-hexahydro-1H-cyclopenta[a]pentalene)]zirconiumdichloride,[7-(3′,6′-di-(1-adamantyl)-fluorene-9′-yl)(5-tert-butyl-7-cylohexyl-2,3,3a,4,7,7a-hexahydro-1H-cyclopenta[a]pentalene)]zirconiumdichloride,[7-(3′,6′-di-tert-butyl-2′,7′-dimethylfluorene-9′-yl)(5-tert-butyl-7-cylohexyl-2,3,3a,4,7,7a-hexahydro-1H-cyclopenta[a]pentalene)]zirconiumdichloride,[7-(octamethylfluorene-12′-yl)(5-tert-butyl-7-cylohexyl-2,3,3a,4,7,7a-hexahydro-1H-cyclopenta[a]pentalene)]zirconiumdichloride,[7-(hexamethyldicyclopentafluorene-10′-yl)(5-tert-butyl-7-cylohexyl-2,3,3a,4,7,7a-hexahydro-1H-cyclopenta[a]pentalene)]zirconiumdichloride,[7-(fluorene-9′-yl)(5-adamantane-1-yl-7-methyl-2,3,3a,4,7,7a-hexahydro-1H-cyclopenta[a]pentalene)]zirconiumdichloride,[7-(2′,7′-di-tert-butylfluorene-9′-yl)(5-adamantane-1-yl-7-methyl-2,3,3a,4,7,7a-hexahydro-1H-cyclopenta[a]pentalene)]zirconiumdichloride, [7-(3′,6′-di-tert-butylfluorene-9′-yl)(5-adamantane-1-yl-7-methyl-2,3,3a,4,7,7a-hexahydro-1H-cyclopenta[a]pentalene)]zirconiumdichloride, [7-(3′,6′-di-(1-adamantyl)-fluorene-9′-yl)(5-adamantane-1-yl-7-methyl-2,3,3a,4,7,7a-hexahydro-1H-cyclopenta[a]pentalene)]zirconiumdichloride,[7-(3′,6′-di-tert-butyl-2′,7′-dimethylfluorene-9′-yl)(5-adamantane-1-yl-7-methyl-2,3,3a,4,7,7a-hexahydro-1H-cyclopenta[a]pentalene)]zirconiumdichloride,[7-(octamethylfluorene-12′-yl)(5-adamantane-1-yl-7-methyl-2,3,3a,4,7,7a-hexahydro-1H-cyclopenta[a]pentalene)]zirconiumdichloride,[7-(hexamethyldicyclopentafluorene-10′-yl)(5-adamantane-1-yl-7-methyl-2,3,3a,4,7,7a-hexahydro-1H-cyclopenta[a]pentalene)]zirconiumdichloride,[7-(fluorene-9′-yl) (5-adamantane-1-yl-7-iso-propyl-2,3,3a,4,7,7a-hexahydro-1H-cyclopenta[a]pentalene)]zirconiumdichloride,[7-(2′,7′-di-tert-butylfluorene-9′-yl)(5-adamantane-1-yl-7-iso-propyl-2,3,3a,4,7,7a-hexahydro-1H-cyclopenta[a]pentalene)]zirconiumdichloride,[7-(3′,6′-di-tert-butylfluorene-9′-yl)(5-adamantane-1-yl-7-iso-propyl-2,3,3a,4,7,7a-hexahydro-1H-cyclopenta[a]pentalene)]zirconiumdichloride,[7-(3′,6′-di-(1-adamantyl)-fluorene-9′-yl)(5-adamantane-1-yl-7-iso-propyl-2,3,3a,4,7,7a-hexahydro-1H-cyclopenta[a]pentalene)]zirconiumdichloride,[7-(3′,6′-di-tert-butyl-2′,7′-dimethylfluorene-9′-yl)(5-adamantane-1-yl-7-iso-propyl-2,3,3a,4,7,7a-hexahydro-1H-cyclopenta[a]pentalene)]zirconiumdichloride,[7-(octamethylfluorene-12′-yl)(5-adamantane-1-yl-7-iso-propyl-2,3,3a,4,7,7a-hexahydro-1H-cyclopenta[a]pentalene)]zirconiumdichloride,and [7-(hexamethyldicyclopentafluorene-10′-yl)(5-adamantane-1-yl-7-iso-propyl-2,3,3a,4,7,7a-hexahydro-1H-cyclopenta[a]pentalene)]zirconiumdichloride.

The transition metal compounds [I] may be titanium derivatives orhafnium derivatives of the above-mentioned compounds. The transitionmetal compounds [I] are not limited to the above-mentioned compounds.

The position numbers used in the nomenclature of the above compoundswill be explained with reference to Formula [I-1] and Formula [I-2]illustrating exemplary enantiomers of[1-(1′,1′,4′,4′,7′,7′,10′,10′-octamethyloctahydrodibenzo[b,h]fluoren-12′-yl)(5-tert-butyl-1-methyl-3-iso-propyl-1,2,3,4-tetrahydropentalene)]zirconiumdichloride and[8-(1′,1′,4′,4′,7′,7′,10′,10′-octamethyloctahydrodibenzo[b,h]fluoren-12′-yl)(2-tert-butyl-8-methyl-3,3b,4,5,6,7,7a,8-octahydrocyclopenta[a]indene)]zirconiumdichloride, respectively.

[Processes for Producing Transition Metal Compounds]

The transition metal compounds used in the invention may be produced byknown processes without limitation. In the following, an example of theprocesses for producing the transition metal compounds [I] used in theinvention will be described. Enantiomers of the compounds maybe producedin the similar manner.

For example, the process for producing the transition metal compound [I]includes a step (1) of preparing a pentalene compound represented byGeneral Formula (1a). The pentalene compound (1a) may be an appropriateisomer having a steric configuration corresponding to the targettransition metal compound [I].

In Formula (1a), R¹, R³, R⁵, R⁶, R⁷ and R⁸ are each independently ahydrogen atom, a hydrocarbon group, a hetero atom-containing hydrocarbongroup, or a silicon-containing group; R² is a hydrocarbon group, ahetero atom-containing hydrocarbon group, or a silicon-containing group;R⁴ is a hydrogen atom; and any two substituents of the substituents R¹to R⁸ except R⁴ may be bonded to each other to form a ring.

Preferred embodiments of the configurations are the same as describedwith respect to General Formula [I].

In an embodiment, the step (1) is followed by a step (2) in which thepentalene compound (1a) is reacted with a fluorene derivative (2a) toform a precursor compound (3a) of a transition metal compound [I], and astep (3) in which a transition metal compound [I] is obtained from theprecursor compound (3a).

<Step (1)>

For example, the pentalene compound (1a) may be synthesized by, asillustrated in Reaction [A], reacting a cyclopentadiene derivative(1a-1) with an α,β-unsaturated carbonyl compound (1a-2); or by, asillustrated in Reaction [B], reacting a cyclopentadiene derivative(1a-1) with a carbonyl compound (1a-3) and an aldehyde compound (1a-4).

In Reaction [A], R¹ to R⁶ and R⁸ are as defined in General Formula [I],and R⁷ is a hydrogen atom. In Reaction [B], R¹ to R⁸ are as defined inGeneral Formula [I]. Preferred embodiments of the configurations are thesame as described with respect to General Formula [I]. The raw materialcompounds may be appropriate isomers having a steric configurationcorresponding to the target pentalene compound (1a).

The cyclopentadiene derivative (1a-1), and the fluorene derivative (2a)and the precursor compound (3a) described later have isomeric formshaving double bonds at different positions in the cyclopentadienyl ring.The reactions here illustrate only one exemplary form of such isomers.The cyclopentadiene derivative (1a-1), and the fluorene derivative (2a)and the precursor compound (3a) described later may be other isomershaving double bonds at different positions in the cyclopentadienyl ring,or may be mixtures of such isomers.

<Reaction [A]>

Based on Reaction [A], the pentalene compound (1a) may be produced byreacting a cyclopentadiene derivative (1a-1) with an α,β-unsaturatedcarbonyl compound (1a-2) under known conditions (see, for example, J.Org. Chem. 1989, 54, 4981-4982).

Alternatively, the pentalene compound (1a) may be produced based onReaction [A] by a process (process A′) in which a cyclopentadienederivative (1a-1) is treated with a base and is allowed to undergo1,4-addition to an α,β-unsaturated carbonyl compound (1a-2) to give aketone or an aldehyde, which is thereafter dehydration condensed.

The base used in the process A′ maybe a conventional base, with examplesincluding alkali metals such as sodium, potassium and lithium; alkalimetal or alkaline earth metal salts such as potassium hydroxide, sodiumhydroxide, potassium carbonate, sodium hydrogen carbonate, bariumhydroxide, sodium alkoxide, potassium alkoxide, magnesium hydroxide,magnesium alkoxide, potassium hydride and sodium hydride;nitrogen-containing bases such as diethylamine, ammonia, pyrrolidine,piperidine, aniline, methylaniline, triethylamine,lithiumdiisopropylamide and sodium amide; organic alkali metal compoundssuch as butyllithium, methyllithium and phenyllithium; and Grignardreagents such as methylmagnesium chloride, methylmagnesium bromide andphenylmagnesium chloride.

The process A′ may involve a catalyst to perform the reaction moreefficiently. The catalyst maybe a conventional catalyst, with examplesincluding phase transfer catalysts, specifically, crown ethers such as18-crown-6-ether and 15-crown-5-ether; cryptands; quaternary ammoniumsalts such as tetrabutylammonium fluoride, methyltrioctylammoniumchloride and tricaprylmethylammonium chloride; phosphonium salts such asmethyltriphenylphosphonium bromide and tetrabutylphosphonium bromide;and chain polyethers. Examples further include halides of magnesium,calcium, lithium, zinc, aluminum, titanium, iron, zirconium, hafnium,boron, tin and rare earths; Lewis acids such as triflates; and acidssuch as acetic acid, trifluoroacetic acid, trifluoromethanesulfonic acidand para-tolylsulfonic acid. In the process A′, the 1,4-additionreaction may be catalyzed by a copper halide such as copper chloride orcopper iodide.

<Reaction [B]>

In Reaction [B], a base and/or a catalyst may be added to perform thereaction more efficiently. The bases and the catalysts which may be usedin Reaction [B] may be similar to those described in Reaction [A].

In Reaction [B], a cyclopentadiene derivative (1a-1) may be reacted witha carbonyl compound (1a-3) and an aldehyde compound (1a-4)simultaneously, or may be reacted with a carbonyl compound (1a-3) and analdehyde compound (1a-4) successively in any order. The carbonylcompound (1a-3) or the aldehyde compound (1a-4) may be converted into anenolate with an agent such as lithium propylamide prior to the reaction,or the reaction may involve an enolate corresponding to the carbonylcompound (1a-3) or the aldehyde compound (1a-4) that is synthesized by aknown method. Alternatively, the carbonyl compound (1a-3) and thealdehyde compound (1a-4) may be subjected to the reaction underdifferent conditions.

The pentalene compound (1a) may be synthesized by other processes suchas those described in Angew. Chem. internal. Edit. 1970, 9, 892-893, J.Am. Chem. SOC. 1985, 107, 5308-5309, and J. Org. Chem. 1990, 55,4504-4506.

Examples of solvents which may be used in Reactions [A] and [B] includeorganic solvents, for example, aliphatic hydrocarbons such as pentane,hexane, heptane, cyclohexane and decalin; aromatic hydrocarbons such asbenzene, toluene and xylene; ethers such as tetrahydrofuran, diethylether, dioxane, 1,2-dimethoxyethane, tert-butyl methyl ether andcyclopentyl methyl ether; halogenated hydrocarbons such asdichloromethane and chloroform; carboxylic acids such as formic acid,acetic acid and trifluoroacetic acid; esters such as ethyl acetate andmethyl acetate; amines, nitriles or nitrogen-containing compounds suchas triethylamine, pyrrolidine, piperidine, aniline, pyridine andacetonitrile; alcohols such as methanol, ethanol, n-propanol,isopropanol, n-butanol, isopropanol, ethylene glycol and methoxyethanol;amides such as N,N-dimethylformamide, N,N-dimethylacetamide,N,N-dimethylimidazolidinone and N-methylpyrrolidone;

dimethyl sulfoxide; sulfur-containing compounds such as carbondisulfide; and ketones such as acetone and methyl ethyl ketone, inparticular, aldehyde and ketone used raw materials; and further includenon-organic solvents such as water and ionic liquids. Mixtures of two ormore of these solvents are also usable. The reaction temperature inReactions [A] and [B] is preferably −100 to 150° C., and more preferably−40 to 120° C.

<Step (2)>

In an embodiment, the step (1) is followed by a step (2) in which thepentalene compound (1a) is reacted with a fluorene derivative (2a) toform a precursor compound (3a) of a transition metal compound [I].

In the above reaction, R¹ to R¹⁶ are as defined in General Formula [I],and L is an alkali metal or an alkaline earth metal. Examples of thealkali metals include lithium, sodium and potassium. Examples of thealkaline earth metals include magnesium and calcium.

The precursor compound (3a) can form a complex in such a manner that thehydrogen atom (R⁴) bonded to the a-position relative to thecyclopentadiene ring comes on the same side as the central metal due toreasons such as the difference in size between R⁴ (hydrogen atom) andR⁵.

The fluorene derivative (2a) may be obtained by a conventional method.

Examples of organic solvents which may be used in the above reactioninclude aliphatic hydrocarbons such as pentane, hexane, heptane,cyclohexane and decalin; aromatic hydrocarbons such as benzene, tolueneand xylene; ethers such as tetrahydrofuran, diethyl ether, dioxane,1,2-dimethoxyethane, tert-butyl methyl ether and cyclopentyl methylether; halogenated hydrocarbons such as dichloromethane and chloroform;and mixtures of two or more of these solvents.

The pentalene compound (1a) and the fluorene derivative (2a) arepreferably reacted in a molar ratio of 10:1 to 1:10, more preferably 2:1to 1:2, and particularly preferably 1.2:1 to 1:1.2. The reactiontemperature is preferably −100 to 150° C., and more preferably −40 to120° C.

An example will be described below in which a transition metal compound[I] is produced from the precursor compound (3a) . The scope of theinvention is not limited to this example, and the transition metalcompound [I] may be produced by any known processes.

<Synthesis of Dialkali Metal Salt>

The precursor compound (3a) is brought into contact with at least onemetal component selected from alkali metals, alkali metal hydrides,alkali metal alkoxides, organic alkali metals and organic alkaline earthmetals, in an organic solvent to give a dialkali metal salt.

Examples of the alkali metals for use in the above reaction includelithium, sodium and potassium. Examples of the alkali metal hydridesinclude sodium hydride and potassium hydride. Examples of the alkalimetal alkoxides include sodium methoxide, potassium ethoxide, sodiumethoxide and potassium-tert-butoxide. Examples of the organic alkalimetals include methyllithium, butyllithium and phenyllithium. Examplesof the organic alkaline earth metals include methylmagnesium halides,butylmagnesium halides and phenylmagnesium halides. Two or more of thesemetal components may be used in combination.

Examples of the organic solvents for use in the above reaction includealiphatic hydrocarbons such as pentane, hexane, heptane, cyclohexane anddecalin; aromatic hydrocarbons such as benzene, toluene and xylene;ethers such as tetrahydrofuran, diethyl ether, dioxane,1,2-dimethoxyethane, tert-butyl methyl ether and cyclopentyl methylether; halogenated hydrocarbons such as dichloromethane and chloroform;and mixtures of two or more of these solvents.

The precursor compound (3a) and the metal component are preferablyreacted in a molar ratio (precursor compound (3a):metal component) of1:1 to 1:20, more preferably 1:1.5 to 1:4, and particularly preferably1:1.8 to 1:2.5. The reaction temperature is preferably −100 to 200° C.,and more preferably −80 to 120° C.

Lewis bases such as tetramethylethylenediamine, and compounds describedin WO 2009/072505 such as a-methylstyrene may be used to promote thereaction.

<Synthesis of Transition Metal Compound>

The dialkali metal salt obtained by the above reaction is reacted with acompound represented by General Formula (4a) in an organic solvent togive a transition metal compound [I].

MZ_(k) . . . (4a)

In Formula (4a) , M is a Group IV transition metal; Zs are eachindependently a halogen atom, a hydrocarbon group, an anionic ligand, ora neutral ligand coordinatable with a lone electron pair; and k is aninteger of 3 to 6. The atoms, groups and the like represented by M and Zare similar to M and Q, respectively, described in General Formula [I].

Examples of the compounds (4a) include titanium (III or IV) fluoride,chloride, bromide and iodide; zirconium (IV) fluoride, chloride, bromideand iodide; hafnium (IV) fluoride, chloride, bromide and iodide; andcomplexes of these halides with ethers such as tetrahydrofuran, diethylether, dioxane and 1,2-dimethoxyethane.

Examples of the organic solvents used in the above reaction include theorganic solvents described in (Synthesis of dialkali metal salt). Thedialkali metal salt and the compound (4a) are preferably reacted in amolar ratio of 10:1 to 1:10, more preferably 2:1 to 1:2, andparticularly preferably 1.2:1 to 1:1.2. The reaction temperature ispreferably −80 to 200° C., and more preferably −75 to 120° C.

<Other Processes>

In another process, the precursor compound (3a) may be reacted directlywith an organometallic reagent such as tetrabenzyltitanium,tetrabenzylzirconium, tetrabenzylhafnium,tetrakis(trimethylsilylmethylene)titanium,tetrakis(trimethylsilylmethylene)zirconium,tetrakis(trimethylsilylmethylene)hafnium, dibenzyldichlorotitanium,dibenzyldichlorozirconium, dibenzyldichlorohafnium, or an amide salt oftitanium, zirconium or hafnium.

The transition metal compound [I] obtained by the aforementionedreaction may be isolated and purified by methods such as extraction,recrystallization and sublimation. The transition metal compound [I]obtained by the aforementioned process may be identified by analyticalmethods such as proton nuclear magnetic resonance spectrometry,¹³C-nuclear magnetic resonance spectrometry, mass analysis and elementalanalysis.

[Olefin Polymerization Catalysts]

The olefin polymerization catalyst used in the invention includes atleast one transition metal compound (A) selected from the transitionmetal compounds represented by General Formula [I] and enantiomersthereof.

Preferably, the olefin polymerization catalyst used in the inventionfurther includes at least one compound (B) selected from organometalliccompounds (B-1), organoaluminum-oxy compounds (B-2), and compounds (B-3)capable of reacting with the transition metal compound (A) to form anion pair (hereinafter, the compound is also written as the “compound(B)”).

More preferably, the olefin polymerization catalyst of the inventionfurther includes a carrier (C) as required.

The olefin polymerization catalyst of the invention may further includean organic compound component (D) as required.

Hereinbelow, the components other than the transition metal compound (A)will be described in detail.

<Compounds (B)<

<<Organometallic compounds (B-1)>>

Examples of the organometallic compounds (B-1) include organometalliccompounds of Group I, II, XII and XIII metals such as organoaluminumcompounds represented by General Formula (B-1a), alkyl complex compoundsof Group I metals and aluminum represented by General Formula (B-1b),and dialkyl compounds of Group II or XII metals represented by GeneralFormula (B-1c).

(B-1a): Ra_(m)Al (ORb)_(n)H_(p)X_(q)

In Formula (B-1a), Ra and Rb are each independently a hydrocarbon grouphaving 1 to 15, preferably 1 to 4 carbon atoms, X is a halogen atom,0<m≦3, 0≦n<3, 0≦p<3, 0≦q<3, and m+n+p+q=3. Examples of theorganoaluminum compounds (B-1a) include trialkylaluminums such astrimethylaluminum, triethylaluminum and triisobutylaluminum;dialkylaluminum hydrides such as diisobutylaluminum hydride; andtricycloalkylaluminums.

(B-1b): M2AlRa₄

In Formula (B-1b), M2 is Li, Na or K, and Ra is a hydrocarbon grouphaving 1 to 15, preferably 1 to 4 carbon atoms. Examples of the alkylcomplex compounds (B-1b) include LiAl (C₂H₅)₄ and LiAl (C₇H₁₅)₄.

(B-1c): RaRbM3

In Formula (B-1c), Ra and Rb are each independently a hydrocarbon grouphaving 1 to 15, preferably 1 to 4 carbon atoms, and M3 is Mg, Zn or Cd.Examples of the compounds (B-1c) include dimethylmagnesium,diethylmagnesium, di-n-butylmagnesium, diethylzinc, di-n-butylzinc anddiphenylzinc.

Of the organometallic compounds (B-1), the organoaluminum compounds(B-1a) are preferred.

The organometallic compounds (B-1) may be used singly, or two or moremay be used in combination.

<<Organoaluminum-Oxy Compounds (B-2)>>

For example, the organoaluminum-oxy compounds (B-2) may be conventionalaluminoxanes, or may be organoaluminum-oxy compounds described inJP-A-H02-78687 which are insoluble or negligibly soluble in benzene. Forexample, the conventional aluminoxanes may be prepared by the followingprocesses (1) to (4) , and are usually obtained as a solution in ahydrocarbon solvent.

(1) An organoaluminum compound such as trialkylaluminum is added to ahydrocarbon medium suspension of a compound containing adsorbed water ora salt containing water of crystallization, for example, magnesiumchloride hydrate, copper sulfate hydrate, aluminum sulfate hydrate,nickel sulfate hydrate or cerous chloride hydrate, thereby reacting theorganoaluminum compound with the adsorbed water or the water ofcrystallization.

(2) Water, ice or water vapor is allowed to act directly on anorganoaluminum compound such as trialkylaluminum in a medium such asbenzene, toluene, diethyl ether or tetrahydrofuran.

(3) An organoaluminum compound such as trialkylaluminum is reacted withan organotin oxide such as dimethyltin oxide or dibutyltin oxide in amedium such as decane, benzene or toluene.

(4) An organoaluminum such as trialkylaluminum is reacted with anorganic compound having a carbon-oxygen bond such as a tertiary alcohol,a ketone or a carboxylic acid, and the resultant compound isnon-hydrolytically converted by thermal decomposition or the like.

The aluminoxane may contain a small amount of organometallic components.After the solvent or the unreacted organoaluminum compound is removed bydistillation from the recovered solution of the aluminoxane, the residuemay be redissolved in a solvent or suspended in a poor solvent for thealuminoxane.

Specific examples of the organoaluminum compounds used in preparing thealuminoxanes include the organoaluminum compounds mentioned above as theorganoaluminum compounds (B-1a). Of those compounds, trialkylaluminumsand tricycloalkylaluminums are preferred, and trimethylaluminum isparticularly preferred.

Examples of the organoaluminum-oxy compounds (B-2) further includemodified methylaluminoxanes. The modified methylaluminoxanes arealuminoxanes prepared from trimethylaluminum and an alkylaluminum otherthan trimethylaluminum. Such compounds are generally called MMAOs. TheMMAOs may be prepared by methods described in U.S. Pat. No. 4,960,878and U.S. Pat. No. 5,041,584. Further, aluminoxanes in which R is anisobutyl group are commercially produced from trimethylaluminum andtriisobutylaluminum by manufacturers such as Toso Finechem Corporation,the compounds being sold under the trade names of MMAO and TMAO.

These MMAOs are aluminoxanes that are improved in solubility in solventsand in storage stability. Specifically, such aluminoxanes arecharacterized in that they are dissolved contrast to the aforementionedaluminoxanes which are insoluble or negligibly soluble in benzene.

Examples of the organoaluminum-oxy compounds (B-2) further includeboron-containing organoaluminum-oxy compounds, halogen-containingaluminoxanes described in WO 2005/066191 and WO 2007/131010, and ionicaluminoxanes described in WO 2003/082879.

The compounds (B-2) may be used singly, or two or more may be used incombination.

<<Compounds (B-3) Capable of Reacting With Transition Metal Compound (A)to Form Ion Pair>>

Examples of the compounds (B-3) capable of reacting with the transitionmetal compound (A) to form an ion pair (hereinafter, also written as“ionic compounds (B-3)”) include Lewis acids, ionic compounds, boranecompounds and carborane compounds described in, for example,JP-A-H01-501950, JP-A-H01-502036, JP-A-H03-179005, JP-A-H03-179006,JP-A-H03-207703, JP-A-H03-207704 and U.S. Pat. No. 5,321,106. Examplesfurther include heteropoly compounds and isopoly compounds. representedby General Formula (B-3a).

Examples of R^(e+) in Formula (B-3a) include H⁺, carbenium cations,oxonium cations, ammonium cations, phosphonium cations,cycloheptyltrienyl cations and ferrocenium cations having transitionmetals. Rf to Ri are each independently an organic group, and preferablyan aryl group.

Examples of the carbenium cations include trisubstituted carbeniumcations such as triphenylcarbenium cation, tris(methylphenyl)carbeniumcation and tris(dimethylphenyl)carbenium cation.

Examples of the ammonium cations include trialkylammonium cations suchas trimethylammonium cation, triethylammonium cation,tri(n-propyl)ammonium cation, triisopropylammonium cation,tri(n-butyl)ammonium cation and triisobutylammonium cation;N,N-dialkylanilinium cations such as N,N-dimethylanilinium cation,N,N-diethylanilinium cation and N,N-2,4,6-pentamethylanilinium cation;and dialkylammonium cations such as diisopropylammonium cation anddicyclohexylammonium cation.

Examples of the phosphonium cations include triarylphosphonium cationssuch as triphenylphosphonium cation, tris(methylphenyl)phosphoniumcation and tris(dimethylphenyl)phosphonium cation.

For example, R^(e+) is preferably a carbenium cation or an ammoniumcation, and particularly preferably triphenylcarbenium cation,N,N-dimethylanilinium cation or N,N-diethylanilinium cation.

Examples of the carbenium salts include triphenylcarbeniumtetraphenylborate, triphenylcarbenium tetrakis(pentafluorophenyl)borate,triphenylcarbenium tetrakis(3,5-ditrifluoromethylphenyl)borate,tris(4-methylphenyl)carbenium tetrakis(pentafluorophenyl)borate andtris(3,5-dimethylphenyl)carbenium tetrakis(pentafluorophenyl)borate.

Examples of the ammonium salts include trialkyl-substituted ammoniumsalts, N,N-dialkylanilinium salts and dialkylammonium salts.

Examples of the trialkyl-substituted ammonium salts includetriethylammonium tetraphenylborate, tripropylammonium tetraphenylborate,tri(n-butyl)ammonium tetraphenylborate, trimethylammoniumtetrakis(p-tolyl)borate, trimethylammonium tetrakis(o-tolyl)borate,tri(n-butyl)ammonium tetrakis(pentafluorophenyl)borate, triethylammoniumtetrakis(pentafluorophenyl)borate, tripropylammoniumtetrakis(pentafluorophenyl)borate, tripropylammoniumtetrakis(2,4-dimethylphenyl)borate, tri(n-butyl)ammoniumtetrakis(3,5-dimethylphenyl)borate, tri(n-butyl)ammoniumtetrakis(4-trifluoromethylphenyl)borate, tri(n-butyl)ammoniumtetrakis(3,5-ditrifluoromethylphenyl)borate, tri(n-butyl)ammoniumtetrakis(o-tolyl)borate, dioctadecylmethylammonium tetraphenylborate,dioctadecylmethylammonium tetrakis(p-tolyl)borate,dioctadecylmethylammonium tetrakis(o-tolyl)borate,dioctadecylmethylammonium tetrakis(pentafluorophenyl)borate,dioctadecylmethylammonium tetrakis(2,4-dimethylphenyl)borate,dioctadecylmethylammonium tetrakis(3,5-dimethylphenyl)borate,dioctadecylmethylammonium tetrakis(4-trifluoromethylphenyl)borate,dioctadecylmethylammonium tetrakis(3,5-ditrifluoromethylphenyl)borate,and dioctadecylmethylammonium.

Examples of the N,N-dialkylanilinium salts include N,N-dimethylaniliniumtetraphenylborate, N,N-dimethylaniliniumtetrakis(pentafluorophenyl)borate, N,N-dimethylaniliniumtetrakis(3,5-ditrifluoromethylphenyl)borate, N,N-diethylaniliniumtetraphenylborate, N,N-diethylaniliniumtetrakis(pentafluorophenyl)borate, N,N-diethylaniliniumtetrakis(3,5-ditrifluoromethylphenyl)borate,N,N-2,4,6-pentamethylanilinium tetraphenylborate, andN,N-2,4,6-pentamethylanilinium tetrakis(pentafluorophenyl)borate.

Examples of the dialkylammonium salts include di(1-propyl)ammoniumtetrakis(pentafluorophenyl)borate, and dicyclohexylammoniumtetraphenylborate.

Further, ionic compounds disclosed by the present applicant (forexample, JP-A-2004-51676) may also be used as the ionic compounds (B-2)without limitation.

The ionic compounds (B-2) may be used singly, or two or more may be usedin combination.

<Carriers (C)>

Examples of the carriers (C) include inorganic or organic compounds inthe form of granular or fine particulate solid. It is preferable to usethe transition metal compound (A) supported on the carrier (C).

<<Inorganic compounds>>

Preferred inorganic compounds as the carriers (C) are porous oxides,inorganic chlorides, clays, clay minerals and ion-exchangeable layeredcompounds.

Examples of the porous oxides include oxides such as SiO₂, Al₂O₃, MgO,ZrO₂, TiO₂, B₂O₃, CaO, ZnO, BaO and ThO₂, and complexes and mixturescontaining these oxides. For example, natural or synthetic zeolites,SiO₂—MgO, SiO₂—Al₂O₃, SiO₂—TiO₂, SiO₂—V₂O₅, SiO₂—Cr₂O₃ and SiO₂—TiO₂—MgOmay be used. Of these, porous oxides containing SiO₂ and/or Al₂O₃ as amain component are preferable.

The porous oxides have different properties depending on types andproduction processes. The carriers that are preferably used in theinvention preferably have a particle diameter of 1 to 300 μm, morepreferably 3 to 100 μm; a specific surface area of 50 to 1300 m²/g, morepreferably 200 to 1200 m²/g; and a pore volume of 0.3 to 3.0 cm³/g, morepreferably 0.5 to 2.0 cm³/g. Where necessary, the carriers may be usedafter being dried and/or calcined at 100 to 1000° C., preferably 150 to700° C. The shapes of the particles are not particularly limited, butspherical particles are particularly preferable.

Examples of the inorganic chlorides include MgCl₂, MgBr₂, MnCl₂ andMnBr₂. The inorganic chlorides may be used as such or may be used afterbeing crushed with a ball mill or an oscillating mill. Further, theinorganic chlorides may be dissolved in solvents such as alcohols and beprecipitated as fine particles with precipitating agents.

The clays are usually composed of clay minerals as main components. Theion-exchangeable layered-compounds are compounds having a crystalstructure in which planes formed by bonds such as ionic bonds arestacked in parallel on top of one another with a weak bond strength, andin which the ions contained therein are exchangeable. Most clay mineralsare ion-exchangeable layered compounds. The clays, the clay minerals andthe ion-exchangeable layered compounds are not limited to naturalproducts but may be synthetic products. Examples of such clays, clayminerals and ion-exchangeable layered compounds include clays, clayminerals and ion crystalline compounds having layered crystal structuressuch as hexagonal closest packed structures, antimony structures, CdCl₂structures and CdI₂ structures.

Examples of the clays and the clay minerals include kaolin, bentonite,kibushi clay, gairome clay, allophane, hisingerite, pyrophyllite, mica,montmorillonite, vermiculite, chlorite, palygorskite, kaolinite,nacrite, dickite, halloysite, pectolite and taeniolite.

Examples of the ion-exchangeable layered compounds include crystallineacid salts of polyvalent metals such as α-Zr(HAsO₄)₂·H₂O, α-Zr(HPO₄)₂,α-Zr(KPO₄)₂·3H₂O, α-Ti(HPO₄)₂, α-Ti (HAsO₄)₂·H₂O, α-Sn (HPO₄)₂·H₂O, γ-Zr(HPO₄)_(2,) γ-Ti(HPO₄)₂ and γ-Ti (NH₄PO₄)₂·H₂O.

It is also preferable that the clays and the clay minerals be subjectedto chemical treatments. Any chemical treatments may be used, withexamples including a surface treatment to remove impurities on thesurface and a treatment to modify the crystal structure of the clay.Specific examples of the chemical treatments include acid treatments,alkali treatments, salt treatments and organic treatments.

Utilizing the ion exchange properties, the spaces between the layers inthe ion-exchangeable layered compounds may be enlarged by exchanging theexchangeable ions between the layers with other larger and bulkier ions.Such bulky ions serve as columns to support the layered structures andare generally called pillars. The introduction of other substancesbetween layers of layered compounds is called intercalation.

Examples of the guest compounds to be intercalated include cationicinorganic compounds such as TiCl₄ and ZrCl₄; metal alkoxides such asTi(OR)₄, Zr(OR)₄, PO(OR)₃ and B(OR)₃ (R is a hydrocarbon group or thelike) ; and metal hydroxide ions such as [Al₁₃O₄(OH)₂₄]⁷⁺, [Zr₄(OH)₁₄]²⁺and [Fe₃O(OCOCH₃)₆]⁺. These compounds may be used singly, or two or moremay be used in combination. The intercalation of the above compounds maybe carried out in the presence of polymers obtained by hydrolysis ofmetal alkoxides such as Si(OR)₄, Al(OR)₃ and Ge(OR)₄ (R is a hydrocarbongroup or the like) or in the presence of colloidal inorganic compoundssuch as SiO₂.

Examples of the pillars include oxides produced by intercalation of theabove metal hydroxide ions between layers followed by thermaldehydration.

Of the carriers (C), porous oxides containing SiO₂ and/or Al₂O₃ as amain component are preferable. The clays and the clay minerals are alsopreferable, and montmorillonite, vermiculite, pectolite, taeniolite andsynthetic mica are particularly preferable.

<<Organic compounds>>

Examples of the organic compounds as the carriers (C) include granularor fine particulate solids having a particle diameter in the range of 5to 300 μm. Specific examples include (co)polymers produced from anα-olefin having 2 to 14 carbon atoms such as ethylene, propylene,1-butene or 4-methyl-1-pentene as a main component; (co)polymersproduced from vinylcyclohexane or styrene as a main component; andmodified products of these polymers.

<Organic compound components (D)>

In the invention, the organic compound component (D) is used as requiredto improve polymerization performance and to enhance properties of theobtainable polymers. Examples of the organic compounds (D) includealcohols, phenolic compounds, carboxylic acids, phosphorus compounds,amides, polyethers and sulfonate salts.

<Use and Sequence of Addition of Components>

In the olefin polymerization, the components may be used and added inappropriately selected manners and orders. For example, the componentsmay be used and added as described below. In the following, thetransition metal compound (A), the compound (B), the carrier (C) and theorganic compound component (D) are also written as “components (A) to(D)”.

(1) The component (A) alone is added to a polymerization reactor.

(2) The component (A) and the component (B) are added to apolymerization reactor in any order.

(3) A catalyst component in which the component (A) is supported on thecomponent (C), and the component (B) are added to a polymerizationreactor in any order.

(4) A catalyst component in which the component (B) is supported on thecomponent (C), and the component (A) are added to a polymerizationreactor in any order.

(5) A catalyst component in which the component (A) and the component(B) are supported on the component (C) is added to a polymerizationreactor.

In the methods (2) to (5), two or more of the catalyst components may bebrought into contact with each other beforehand. In the methods (4) and(5) in which the component (B) is supported, an unsupported component(B) may be added in any order as required. In this case, the components(B) may be the same as or different from each other. Further, an olefinmaybe prepolymerized on the solid catalyst component in which thecomponent (A) is supported on the component (C), and the solid catalystcomponent in which the component (A) and the component (B) are supportedon the component (C). Furthermore, an additional catalyst component maybe supported on the prepolymerized solid catalyst component.

[Olefin Polymer Production Processes]

The olefin polymer production process of the present invention includesa step of polymerizing at least one olefin

A selected from ethylene and α-olefins having 4 to 30 carbon atomsoptionally with propylene in the presence of the olefin polymerizationcatalyst described above. Here, the term “polymerization” is used as acollective term including homopolymerization and copolymerization.Further, the meaning of the phrase “olefins are polymerized in thepresence of the olefin polymerization catalyst” includes embodiments inwhich olefins are polymerized while the components of the olefinpolymerization catalyst are added to the polymerization reactor in anappropriate manner as described in the methods (1) to (5) above.

In the invention, the polymerization may be carried out by any ofliquid-phase polymerization methods such as solution polymerization andsuspension polymerization, and gas-phase polymerization methods.Examples of inert hydrocarbon solvents used in the liquid-phasepolymerization methods include aliphatic hydrocarbons such as propane,butane, pentane, hexane, heptane, octane, decane, dodecane and kerosine;alicyclic hydrocarbons such as cyclopentane, cyclohexane andmethylcyclopentane; aromatic hydrocarbons such as benzene, toluene andxylene; and halogenated hydrocarbons such as ethylene chloride,chlorobenzene and dichloromethane. The inert hydrocarbon solvents may beused singly, or two or more may be used in combination. A so-called bulkpolymerization method may be used in which the liquefied olefin suppliedto the polymerization itself is used as the solvent.

In the polymerization of olefins using the olefin polymerizationcatalyst, the components that form the olefin polymerization catalystmay be used in the following amounts. In the olefin polymerizationcatalyst, the contents of the components may be controlled as describedbelow.

The component (A) is usually used in an amount of 10⁻¹⁰ to 10⁻² mol, andpreferably 10⁻⁸ to 10⁻³ mol per liter of the reaction volume. Thecomponent (B-1) may be used in such an amount that the molar ratio[(B-1)/M] of the component (B-1) to all the transition metal atoms (M)in the component (A) is usually 1 to 50,000, preferably 10 to 20,000,and particularly preferably 50 to 10,000. The component (B-2) may beused in such an amount that the molar ratio [Al/M] of the aluminum atomsin the component (B-2) to all the transition metal atoms (M) in thecomponent (A) is usually 10 to 5,000, and preferably 20 to 2,000. Thecomponent (B-3) may be used in such an amount that the molar ratio[(B-3)/M] of the component (B-3) to all the transition metal atoms (M)in the component (A) is usually 1 to 1000, and preferably 1 to 200.

When the component (C) is used, the amount thereof may be preferablysuch that the weight ratio [(A)/(C)] of the component (A) to thecomponent (C) is 0.0001 to 1, more preferably 0.0005 to 0.5, and stillmore preferably 0.001 to 0.1.

When the component (D) is used, the amount thereof may be such that,when the component (B) is the component (B-1), the molar ratio[(D)/(B-1)] is usually 0.01 to 10, and preferably 0.1 to 5; when thecomponent (B) is the component (B-2), the molar ratio [(D)/(B-2)] isusually 0.005 to 2, and preferably 0.01 to 1; and when the component (B)is the component (B-3), the molar ratio [(D)/(B-3)] is usually 0.01 to10, and preferably 0.1 to 5.

In the production process of the invention, the olefin polymerizationtemperature is usually −50 to +200° C., and preferably 0 to 180° C.; andthe polymerization pressure is usually atmospheric pressure to 10 MPaG,and preferably atmospheric pressure to 5 MPaG. The polymerizationreaction may be carried out batchwise, semi-continuously orcontinuously. The polymerization may be carried out in two or morestages under different reaction conditions. The molecular weight of theobtainable olefin polymers may be adjusted by the presence of hydrogenand so on in the polymerization system, by controlling thepolymerization temperature, or by controlling the amount of thecomponent (B) used.

The production process of the invention can produce olefin polymerswhich have high stereoregularity, high melting point and high molecularweight, in such a manner that high catalytic activity is maintained evenunder industrially advantageous high-temperature conditions. Under suchhigh-temperature conditions, the polymerization temperature is usually40° C. or above, preferably 40 to 200° C., more preferably 45 to 150°C., and particularly preferably 50 to 150° C. (In other words, thepolymerization temperature is particularly preferably a temperature atwhich industrial production is feasible.)

In particular, hydrogen is a preferred additive which may enhance thepolymerization activity of the catalyst and may increase or decrease themolecular weight of polymers. When hydrogen is added to the system, theamount thereof is appropriately about 0.00001 to 100 NL per 1 mol of theolefin.

The hydrogen concentration in the system may be controlled by adjustingthe amount of hydrogen supplied, or also by performing a reaction in thesystem which generates or consumes hydrogen, by separating hydrogen withuse of a membrane, or by discharging part of the gas containing hydrogenout of the system.

Olefin polymers synthesized by the inventive production process may besubjected to known post treatment steps such as catalyst deactivationstep, residual catalyst removal step and drying step as required.

<Olefins>

The olefin supplied to the polymerization reaction in the inventiveproduction process is at least one olefin A selected from ethylene andα-olefins having 4 to 30 carbon atoms, which may be used in combinationwith propylene as needed.

The olefin is an a-olefin having 4 to 30 carbon atoms, more preferablyan a-olefin having 4 to 20 carbon atoms, and is particularly preferablyan a-olefin having 4 to 10 carbon atoms.

Examples of the a-olefins include linear or branched α-olefins. Examplesof the linear or branched α-olefins include 1-butene, 2-butene,1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene,3-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene,1-hexadecene, 1-heptadecene, 1-octadecene and 1-eicosene.

The polymerization may be performed in the presence of at least oneselected from cyclic olefins, polar group-containing olefins,hydroxyl-terminated vinyl compounds and aromatic vinyl compounds in thereaction system. Further, the polymerization may involve polyenes.Additional monomers such as vinylcyclohexane may be copolymerizedwithout departing from the spirit of the invention.

Examples of the cyclic olefins include cyclopentene, cycloheptene,norbornene, 5-methyl-2-norbornene, tetracyclododecene and2-methyl-1,4,5,8-dimethano-1,2,3,4,4a,5,8,8a-octahydronaphthalene.

Examples of the polar group-containing olefins include α,β-unsaturatedcarboxylic acids such as acrylic acid, methacrylic acid, fumaric acid,maleic anhydride, itaconic acid, itaconic anhydride andbicyclo(2,2,1)-5-heptene-2,3-dicarboxylic anhydride, and metal saltsthereof such as sodium salts, potassium salts, lithium salts, zincsalts, magnesium salts, calcium salts and aluminum salts;

α,β-unsaturated carboxylate esters such as methyl acrylate, ethylacrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate,isobutyl acrylate, tert-butyl acrylate, 2-ethylhexyl acrylate, methylmethacrylate, ethyl methacrylate, n-propyl methacrylate, isopropylmethacrylate, n-butyl methacrylate and isobutyl methacrylate;

vinyl esters such as vinyl acetate, vinyl propionate, vinyl caproate,vinyl caprate, vinyl laurate, vinyl stearate and vinyl trifluoroacetate;and unsaturated glycidyls such as glycidyl acrylate, glycidylmethacrylate and itaconic acid monoglycidyl ester.

Examples of the hydroxyl-terminated vinyl compounds include linearhydroxyl-terminated vinyl compounds such as hydroxylated-1-butene,hydroxylated-1-pentene, hydroxylated-1-hexene, hydroxylated-1-octene,hydroxylated-1-decene, hydroxylated-1-undecene, hydroxylated-1-dodecene,hydroxylated-1-tetradecene, hydroxylated-1-hexadecene,hydroxylated-1-octadecene and hydroxylated-1-eicosene; and branchedhydroxyl-terminated vinyl compounds such ashydroxylated-3-methyl-1-butene, hydroxylated-3-methyl-1-pentene,hydroxylated-4-methyl-1-pentene, hydroxylated-3-ethyl-1-pentene,hydroxylated-4,4-dimethyl-1-pentene, hydroxylated-4-methyl-1-hexene,hydroxylated-4,4-dimethyl-1-hexene, hydroxylated-4-ethyl-1-hexene andhydroxylated-3-ethyl-1-hexene.

Examples of the aromatic vinyl compounds include styrene; mono- orpolyalkylstyrenes such as o-methylstyrene, m-methylstyrene,p-methylstyrene, o,p-dimethylstyrene, o-ethylstyrene, m-ethylstyrene andp-ethylstyrene; functional group-containing styrene derivatives such asmethoxystyrene, ethoxystyrene, vinylbenzoic acid, methyl vinylbenzoate,vinyl benzyl acetate, hydroxystyrene, o-chlorostyrene, p-chlorostyreneand divinylbenzene; 3-phenylpropylene, 4-phenylpropylene anda-methylstyrene.

The polyenes are preferably selected from dienes and trienes. In apreferred embodiment, the polyene is used in the range of 0.0001 to 1mol % relative to all the olefins supplied to the polymerizationreaction.

Examples of the dienes include α,ω-nonconjugated dienes such as1,4-pentadiene, 1,5-hexadiene, 1,4-hexadiene, 1,4-octadiene,1,5-octadiene, 1,6-octadiene, 1,7-octadiene and 1,9-decadiene;nonconjugated dienes such as ethylidenenorbornene, vinylnorbornene,dicyclopentadiene, 7-methyl-1,6-octadiene and4-ethylidene-8-methyl-1,7-nonadiene; and conjugated dienes such asbutadiene and isoprene. Of these, the a,w-nonconjugated dienes anddienes having a norbornene skeleton are preferred.

Examples of the trienes include nonconjugated trienes such as6,10-dimethyl-1,5,9-undecatriene, 4,8-dimethyl-1,4,8-decatriene,5,9-dimethyl-1,4,8-decatriene, 6,9-dimethyl-1,5,8-decatriene,6,8,9-trimethyl-1,5,8-decatriene, 6-ethyl-10-methyl-1,5,9-undecatriene,4-ethylidene-1,6,-octadiene, 7-methyl-4-ethylidene-1,6-octadiene,4-ethylidene-8-methyl-1,7-nonadiene (EMND),7-methyl-4-ethylidene-1,6-nonadiene, 7-ethyl-4-ethylidene-1,6-nonadiene,6,7-dimethyl-4-ethylidene-1,6-octadiene,6,7-dimethyl-4-ethylidene-1,6-nonadiene, 4-ethylidene-1,6-decadiene,7-methyl-4-ethylidene-1,6-decadiene,7-methyl-6-propyl-4-ethylidene-1,6-octadiene,4-ethylidene-1,7-nonadiene, 8-methyl-4-ethylidene-1,7-nonadiene and4-ethylidene-1,7-undecanediene; and conjugated trienes such as1,3,5-hexatriene. Of these, nonconjugated trienes having a double bondat an end, 4,8-dimethyl-1,4,8-decatriene and4-ethylidene-8-methyl-1,7-nonadiene (EMND) are preferable.

The dienes or trienes may be used singly, or two or more maybe used incombination. Further, the dienes and the trienes may be used incombination. Of the polyenes, the α,ω-nonconjugated dienes and thepolyenes having a norbornene skeleton are preferred.

In the olefin polymer production process of the invention, it is morepreferable that at least one of the olefin(s) A be ethylene, 1-butene,4-methyl-1-pentene, 1-hexene, 1-octene or 1-decene. Particularlypreferably, the polymerization is ethylene homopolymerization,ethylene/propylene copolymerization, ethylene/1-butene copolymerization,1-butene homopolymerization, 1-butene/ethylene copolymerization,1-butene/propylene copolymerization, 1-butene/1-hexene copolymerization,1-butene/1-octene copolymerization, ethylene/1-butene/propylenecopolymerization, ethylene/1-butene/1-octene copolymerization,4-methyl-1-pentene homopolymerization, 4-methyl-1-pentene/propylenecopolymerization, 4-methyl-1-pentene/1-hexene copolymerization,4-methyl-1-pentene/1-octene copolymerization,4-methyl-1-pentene/1-decene copolymerization,4-methyl-1-pentene/1-hexadecene copolymerization,4-methyl-1-pentene/1-heptadecene copolymerization,4-methyl-1-pentene/1-octadecene copolymerization,4-methyl-1-pentene/1-hexadecene/1-octadecene copolymerization, 1-decenehomopolymerization, 1-decene/1-octene copolymerization,1-decene/1-dodecene copolymerization, or 1-decene/1-octene/1-dodecenecopolymerization.

In the case where the optional propylene is used, the at least oneolefin A selected from ethylene and a-olefins having 4 to 30 carbonatoms, and the propylene are used in such amounts that the olefin(s)A:propylene ratio (by mol) is usually 1:100 to 5000:1, and preferably1:50 to 1000:1.

[Olefin Polymers]

The olefin polymers of the invention may be obtained by polymerizing atleast one olefin A selected from ethylene and a-olefins having 4 to 30carbon atoms, and optionally propylene in the presence of theaforementioned olefin polymerization catalyst.

The olefin polymer of the invention contains constituent units derivedfrom the at least one selected from ethylene and a-olefins having 4 to30 carbon atoms in a total amount of from more than 50 mol % to 100 mol%, preferably from 55 to 100 mol %, and still more preferably from 70 to100 mol %, and constituent units derived from propylene in an amount offrom 0 mol % to less than 50 mol %, preferably 0 to 45 mol %, and stillmore preferably 0 to 30 mol %. Here, the content of the constituentunits derived from the at least one selected from ethylene and a-olefinshaving 4 to 30 carbon atoms and the content of the constituent unitsderived from propylene total 100 mol %.

The contents of these units may be determined by nuclear magneticresonance spectroscopy or, in the case where there is a referencesubstance, by a method such as infrared spectroscopy. The same appliesto the novel 1-butene polymers and 4-methyl-1-pentene polymers describedlater.

The olefin polymer of the invention preferably contains constituentunits derived from at least one selected from ethylene, 1-butene,4-methyl-1-pentene, 1-hexene, 1-octene and 1-decene in a total amount ofmore than 50 mol %. More specifically, examples of such polymers includeethylene homopolymers, ethylene/propylene copolymers, ethylene/l-butenecopolymers, 1-butene homopolymers, 1-butene/ethylene copolymers,1-butene/propylene copolymers, 1-butene/1-hexene copolymers,1-butene/1-octene copolymers, ethylene/1-butene/propylene copolymers,ethylene/1-butene/1-octene copolymers, 4-methyl-1-pentene homopolymers,4-methyl-1-pentene/propylene copolymers, 4-methyl-1-pentene/1-hexenecopolymers, 4-methyl-1-pentene/1-octene copolymers,4-methyl-1-pentene/1-decene copolymers, 4-methyl-1-pentene/1-hexadecenecopolymers, 4-methyl-1-pentene/1-heptadecene copolymers,4-methyl-1-pentene/1-octadecene copolymers,4-methyl-1-pentene/1-hexadecene/1-octadecene copolymers, 1-decenehomopolymers, 1-decene/1-octene copolymers, 1-decene/1-dodecenecopolymers and 1-decene/1-octene/1-dodecene copolymers.

Of these polymers, particularly preferred polymers are 1-butene polymerscontaining more than 50 mol % of constituent units derived from1-butene, and 4-methyl-1-pentene polymers containing more than 50 mol %of constituent units derived from 4-methyl-1-pentene.

In the olefin polymers of the invention, the weight-average molecularweight measured by gel permeation chromatography (GPC) is preferably10,000 to 5,000,000, more preferably 50,000 to 3,000,000, andparticularly preferably 100,000 to 2,500,000. The ratio of theweight-average molecular weight (Mw) to the number-average molecularweight (Mn), namely, the molecular weight distribution (Mw/Mn) ispreferably 1.0 to 8.0, more preferably 1.5 to 5.0, and particularlypreferably 1.8 to 3.5.

In the olefin polymers of the invention, the intrinsic viscosity [η] ispreferably 0.1 to 20 dl/g, more preferably 0.3 to 10 dl/g, and stillmore preferably 0.5 to 8 dl/g.

In the olefin polymers of the invention, the stereoregularity of theα-olefin-derived constituent units is preferably isotactic orhemiisotactic. More preferably, the meso diad fraction measured by¹³C-NMR is not less than 70%, still more preferably not less than 80%,further preferably not less than 90%, and particularly preferably notless than 95%.

Details of the measurements of these properties are described inExamples.

With the aforementioned configurations and properties (in particular,high stereoregularity), the olefin polymers of the invention arecrystalline olefin polymers exhibiting high melting point, high heatresistance and high mechanical properties such as high rigidity and highstrength, or amorphous or low-crystalline olefin polymers exhibitingboth viscous properties and elastic properties.

The olefin polymers of the invention may be partially graft-modifiedwith polar monomers. Examples of such polar monomers include hydroxylgroup-containing ethylenically unsaturated compounds, aminogroup-containing ethylenically unsaturated compounds, epoxygroup-containing ethylenically unsaturated compounds, aromatic vinylcompounds, unsaturated carboxylic acids or derivatives thereof, vinylester compounds, vinyl chlorides, vinyl group-containing organosiliconcompounds and carbodiimide compounds.

Particularly preferred polar monomers are unsaturated carboxylic acidsor derivatives thereof, and vinyl group-containing organosiliconcompounds.

Examples of the unsaturated carboxylic acids or derivatives thereofinclude unsaturated compounds having one or more carboxyl groups, estersof carboxyl compounds with alkyl alcohols, and unsaturated compoundshaving one or more carboxylic anhydride groups. Examples of theunsaturated groups include vinyl groups, vinylene groups and unsaturatedcyclic hydrocarbon groups. These compounds may be any known compoundswithout limitation. Specific examples include unsaturated carboxylicacids such as (meth)acrylic acid, maleic acid, fumaric acid,tetrahydrophthalic acid, itaconic acid, citraconic acid, crotonic acid,isocrotonic acid and nadic acid [trade name](endocis-bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid); and derivatives thereof such as acidhalides, amides, imides, anhydrides and esters. Specific examples ofsuch derivatives include methyl acrylate, methyl methacrylate, dimethylmaleate, monomethyl maleate, dimethyl fumarate, dimethyl itaconate,diethyl citraconate, dimethyl tetrahydrophthalate, dimethyl nadicate(dimethyl endocis-bicyclo[2,2,1] hept-5-ene-2,3-dicarboxylate), malenylchloride, maleimide, maleic anhydride, citraconic anhydride, monomethylmaleate, dimethyl maleate and glycidyl maleate. These unsaturatedcarboxylic acids and derivatives thereof may be used singly, or two ormore may be used in combination. Of these compounds, unsaturateddicarboxylic acids or acid anhydrides thereof are preferred. Inparticular, maleic acid, nadic acid [trade name] and acid anhydridesthereof are preferably used.

The vinyl group-containing organosilicon compounds may be any known suchcompounds without limitation. Specific examples includevinyltriethoxysilane, vinyltrimethoxysilane,vinyltris(β-methoxy-ethoxysilane), γ-glycidoxypropyltrimethoxysilane,γ-aminopropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane,2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane,3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethylethoxysilane,p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane,3-methacryloxypropylmethyldiethoxysilane,3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane,N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane,N-2-(aminoethyl)-3-aminopropyltrimethoxysilane,N-2-(aminoethyl)-3-aminopropyltriethoxysilane,3-aminopropyltrimethoxysilane,3-triethoxysilyl-N-(1,3-dimethyl-butylidene)propylamine,N-phenyl-3-aminopropyltrimethoxysilane, 3-ureidopropyltriethoxysilaneand 3-isocyanatopropyltriethoxysilane.γ-Glycidoxypropyltrimethoxysilane, γ-aminopropyltriethoxysilane,γ-methacryloxypropyltrimethoxysilane, vinyltriethoxysilane,vinyltrimethoxysilane and 3-acryloxypropyltrimethoxysilane arepreferable. Vinyltriethoxysilane, vinyltrimethoxysilane and3-acryloxypropyltrimethoxysilane having small steric hindrance and highgraft modification efficiency are more preferable.

The polar monomer is usually used in an amount of 1 to 100 parts byweight, and preferably 5 to 80 parts by weight per 100 parts by weightof the olefin polymer of the invention.

The polar monomers may be used singly, or two or more may be used incombination.

The graft polymerization is usually performed in the presence of aradical initiator.

Examples of the radical initiators include organic peroxides and azocompounds. Any known such compounds may be used, with specific examplesincluding dialkyl peroxides such as dicumyl peroxide, di-t-butylperoxide, di-t-butyl peroxy-3, 3, 5-trimethylcyclohexane, t-butylcumylperoxide, di-t-amyl peroxide, t-butyl hydroperoxide, 2, 5-dimethyl-2,5-di (t-butylperoxy) hexyne-3, 2,5-dimethyl-2,5-di(benzoylperoxy)hexane, 2, 5-dimethyl-2, 5-di(t-butylperoxy) hexane and α,α′-bis(t-butylperoxy-m-isopropyl)benzene;peroxyesters such as t-butyl peroxyacetate, t-butyl peroxyisobutyrate,t-butyl peroxypivalate, t-butyl peroxymaleate, t-butylperoxyneodecanoate, t-butyl peroxybenzoate and di-t-butylperoxyphthalate; ketone peroxides such as dicyclohexanone peroxide; andmixtures thereof.

The radical initiator may be directly mixed together with the polymerand the polar monomer, or may be used after being dissolved in a smallamount of an organic solvent. The organic solvent is not particularlylimited as long as the organic solvent can dissolve the radicalinitiator.

The graft polymerization of the polar monomer may involve a reductivesubstance. The use of a reductive substance may increase the amount inwhich the polar monomer is grafted.

The graft modification maybe performed by a known method. For example,the polymer may be dissolved in an organic solvent, then the additivessuch as the polar monomer and the radical initiator may be added to thesolution, and the reaction may be performed at 60 to 260° C., preferably80 to 200° C. for 0.5 to 15 hours, preferably 1 to 10 hours.

Alternatively, the polymer and the polar monomer may be reacted witheach other in the absence of solvents in a device such as an extruder.The reaction in this case is desirably performed at a temperature thatis usually not less than the melting point of the polymer, specifically,at a temperature of 120 to 300° C. for 0.5 to 10 minutes.

The amount of modification (the amount of the polar monomer grafted) inthe polymer obtained by the above method is usually 0.1 to 50 wt %,preferably 0.2 to 30 wt %, and more preferably 0.2 to 10 wt % relativeto 100 wt % of the graft-modified polymer.

When the polymer in the invention includes graft-modified molecules,excellent adhesion and compatibility with respect to other resins may beobtained and the wettability of the surface of shaped articles may beimproved. By being crosslinked, the graft-modified polymer may besuitably used in crosslinked electric wires and crosslinked pipes.

The olefin polymer of the invention may be halogenated. The halogenatedolefin polymer may be used as a macro initiator, and a radicallypolymerizable monomer may be polymerized therewith by atom transferradical polymerization to produce a block graft copolymer which has apolyolefin segment and a polar polymer segment chemically bonded to eachother. The macro initiator is a polymer having an ability to initiateatom transfer radical polymerization, and has a site in the molecularchain which serves as a starting point of atom transfer radicalpolymerization.

The halogenated olefin polymer is produced by reacting the olefinpolymer of the invention with a halogenating agent. The halogenatingagents are not particularly limited as long as they can halogenate theinventive olefin polymers into halogenated olefin polymers. Specificexamples include chlorine, bromine, iodine, phosphorus trichloride,phosphorus tribromide, phosphorus triiodide, phosphorus pentachloride,phosphorus pentabromide, phosphorus pentaiodide, thionyl chloride,sulfuryl chloride, thionyl bromide, N-chlorosuccinimide,N-bromosuccinimide, N-bromocaprolactam, N-bromophthalimide,1,3-dibromo-5,5-dimethylhydantoin, N-chloroglutarimide,N-bromoglutarimide, N,N′-dibromoisocyanuric acid, N-bromoacetamide,N-bromocarbamic acid esters, dioxane dibromide, phenyltrimethylammoniumtribromide, pyridinium hydrobromide perbromide, pyrrolidonehydrotribromide, t-butyl hypochlorite, t-butyl hypobromite, copper (II)chloride, copper (II) bromide, iron (III) chloride, oxalyl chloride andIBr. Of these, preferred agents are chlorine, bromine,N-chlorosuccinimide, N-bromosuccinimide, N-bromocaprolactam,N-bromophthalimide, 1,3-dibromo-5,5-dimethylhydantoin,N-chloroglutarimide, N-bromoglutarimide and N,N′-dibromoisocyanuricacid, and more preferred agents are bromine and compounds having a N-Brbond such as N-bromosuccinimide, N-bromocaprolactam, N-bromophthalimide,1,3-dibromo-5,5-dimethylhydantoin, N-bromoglutarimide andN,N′-dibromoisocyanuric acid.

The reaction between the olefin polymer of the invention and thehalogenating agent is preferably performed in an inert gas atmosphere.Examples of the inert gases include nitrogen, argon and helium. Thereaction may involve a solvent as required. Any solvents that do notinhibit the reaction may be used, with examples including aromatichydrocarbon solvents such as benzene, toluene and xylene; aliphatichydrocarbon solvents such as pentane, hexane, heptane, octane, nonaneand decane; alicyclic hydrocarbon solvents such as cyclohexane,methylcyclohexane and decahydronaphthalene; chlorinated hydrocarbonsolvents such as chlorobenzene, dichlorobenzene, trichlorobenzene,methylene chloride, chloroform, carbon tetrachloride,tetrachloroethylene and tetrachloroethane; alcohol solvents such asmethanol, ethanol, n-propanol, iso-propanol, n-butanol, sec-butanol andtert-butanol; ketone solvents such as acetone, methyl ethyl ketone andmethyl isobutyl ketone; ester solvents such as ethyl acetate anddimethyl phthalate; and ether solvents such as dimethyl ether, diethylether, di-n-amyl ether, tetrahydrofuran and dioxyanisole.

The halogenation reaction may involve a radical initiator as required topromote the reaction. Examples of the radical initiators include thoseradical initiators described hereinabove.

The olefin polymer of the invention and the halogenating agent may bereacted by any of various known methods. For example, the olefin polymermay be suspended or dissolved in a solvent, and the halogenating agentand optionally additives such as the radical initiator may be admixedwith the suspension or solution followed by the reaction at atemperature of −80° C. to 250° C., preferably a temperature of from roomtemperature to the boiling point of the solvent. Alternatively, theolefin polymer may be brought into contact with the halogenating agentand optionally the radical initiator by melt kneading at a temperatureof not less than the melting point of the olefin polymer, for example, atemperature of 180 to 300° C.

The polar polymer segment is a homopolymer or a copolymer of one or moremonomers selected from radically polymerizable monomers. Specificexamples of the radically polymerizable monomers include (meth)acrylicacid monomers such as (meth)acrylic acid, methyl (meth)acrylate, ethyl(meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate,n-butyl (meth)acrylate, isobutyl (meth) acrylate, tert-butyl (meth)acrylate, n-pentyl (meth)acrylate, n-hexyl (meth)acrylate, cyclohexyl(meth)acrylate, n-heptyl (meth)acrylate, n-octyl (meth)acrylate,2-ethylhexyl (meth)acrylate, nonyl (meth)acrylate, decyl (meth)acrylate,dodecyl (meth)acrylate, phenyl (meth)acrylate, toluyl (meth)acrylate,benzyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 3-methoxybutyl(meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth)acrylate, stearyl (meth) acrylate, glycidyl (meth)acrylate, 2-aminoethyl(meth)acrylate, 2-(dimethylamino)ethyl (meth) acrylate,γ-(methacryloyloxypropyl)trimethoxysilane, ethylene oxide adduct of(meth)acrylic acid, trifluoromethylmethyl (meth) acrylate,2-trifluoromethylethyl (meth) acrylate, 2-perfluoroethylethyl (meth)acrylate, 2-perfluoroethyl-2-perfluorobutylethyl (meth)acrylate,2-perfluoroethyl (meth) acrylate, perfluoromethyl (meth) acrylate,diperfluoromethylmethyl (meth) acrylate,2-perfluoromethyl-2-perfluoroethylmethyl (meth) acrylate,2-perfluorohexylethyl (meth) acrylate, 2-perfluorodecylethyl(meth)acrylate and 2-perfluorohexadecylethyl (meth) acrylate; styrenemonomers such as styrene, vinyltoluene, α-methylstyrene, chlorostyrene,styrenesulfonic acid and salts thereof; fluorine-containing vinylmonomers such as perfluoroethylene, perfluoropropylene and vinylidenefluoride; silicon-containing vinyl monomers such asvinyltrimethoxysilane and vinyltriethoxysilane; maleic anhydride, maleicacid, and monoalkyl esters and dialkyl esters of maleic acid; fumaricacid, and monoalkyl esters and dialkyl esters of fumaric acid; maleimidemonomers such as maleimide, methylmaleimide, ethylmaleimide,propylmaleimide, butylmaleimide, hexylmaleimide, octylmaleimide,dodecylmaleimide, stearylmaleimide, phenylmaleimide andcyclohexylmaleimide; nitrile group-containing vinyl monomers such asacrylonitrile and methacrylonitrile; amide group-containing vinylmonomers such as (meth)acrylamide, N-methyl(meth)acrylamide,N-ethyl(meth)acrylamide, N-propyl(meth)acrylamide,N-isopropyl(meth)acrylamide, N-butyl(meth)acrylamide andN,N-dimethyl(meth)acrylamide; vinyl ester monomers such as vinylacetate, vinyl propionate, vinyl pivalate, vinyl benzoate and vinylcinnamate; vinyl chloride, vinylidene chloride, allyl chloride and allylalcohols. These organic compounds may be used singly, or two or more maybe used in combination.

The atom transfer radical polymerization may be performed by a knownmethod. The polymerization method is not particularly limited, and anymethods such as bulk polymerization, solution polymerization, suspensionpolymerization, emulsion polymerization and bulk suspensionpolymerization may be used. The reaction temperature is not particularlylimited as long as the temperature allows the radical polymerizationreaction to proceed. The polymerization temperature is usually −100° C.to 250° C., but may be variable depending on the desired degree ofpolymerization of the polymer, and the types and the amounts of theradical initiator and the solvent used.

The olefin polymers of the invention may contain additives as requiredwhile still achieving the objects of the invention. Examples of theadditives include weather stabilizers, heat stabilizers, antistaticagents, slip agents, anti-blocking agents, foaming agents,crystallization auxiliaries, antifogging agents, (transparent)nucleating agents, lubricants, pigments, dyes, plasticizers, anti-agingagents, hydrochloric acid absorbers, antioxidants, releasing agents,impact improvers, anti-UV agents (UV ray absorbers), fillers,crosslinking agents, co-crosslinking agents, crosslinking auxiliaries,tackifiers, softeners, flame-retardants and processing aids. The amountof the additives is not particularly limited, but is usually 0 to 50parts by weight, preferably 0 to 30 parts by weight, still morepreferably 0 to 10 parts by weight, and particularly preferably 0 to 1part by weight per 100 parts by weight of the olefin polymer.

The antioxidants may be any of known antioxidants. Specific examplesinclude hindered phenol compounds, sulfur antioxidants, lactoneantioxidants, organic phosphite compounds, organic phosphonitecompounds, and combinations of these compounds.

The nucleating agents may be any of known nucleating agents, and may beused to further improve the process-ability of the olefin polymers,namely, to further increase the crystallization temperature and thecrystallization rate. Specific examples include dibenzylidenesorbitolnucleating agents, phosphate ester salt nucleating agents, rosinnucleating agents, metal benzoate salt nucleating agents, fluorinatedpolyethylenes, sodium 2,2-methylenebis(4,6-di-t-butylphenyl)phosphate,pimelic acid and salts thereof, and 2,6-naphthalene acid dicarboxylicacid dicyclohexylamide. The amount of the nucleating agents is notparticularly limited, but is preferably 0.1 to 1 part by weight per 100parts by weight of the olefin polymer. The nucleating agents maybe addedat appropriate time, for example, during or after the polymerization orduring shaping.

The lubricants may be any of known lubricants. Specific examples includesodium salts, calcium salts and magnesium salts of saturated orunsaturated fatty acids such as lauric acid, palmitic acid, oleic acidand stearic acid. These lubricants may be used singly, or two or moremay be used in combination. The amount of the lubricants is notparticularly limited, but is usually about 0.1 to 3 parts by weight, andpreferably about 0.1 to 2 parts by weight per 100 parts by weight of thepolymer composition.

The slip agents may be any of known slip agents. Specifically, it ispreferable to use amides of saturated or unsaturated fatty acids such aslauric acid, palmitic acid, oleic acid, stearic acid, erucic acid andbehenic acid, or bisamides of these saturated or unsaturated fattyacids. Of these, erucamide and ethylenebisstearamide are particularlypreferable. These fatty acid amides are preferably added in the range of0.01 to 5 parts by weight per 100 parts by weight of the polymercomposition.

The anti-blocking agents may be any of known anti-blocking agents.Specific examples include fine powdery silicas, fine powdery aluminumoxides, fine powdery clays, powdery or liquid silicon resins,tetrafluoroethylene resins, and fine powdery crosslinked resins such ascrosslinked acrylic and methacrylic resin powders. Of these, finepowdery silicas and crosslinked acrylic and methacrylic resin powdersare preferable.

The softeners may be any of known softeners. Specific examples includepetroleum substances such as process oils, lubricating oils, paraffins,liquid paraffins, polyethylene waxes, polypropylene waxes, petroleumasphalts and vaselines; coal tars such as coal tars and coal tarpitches; fatty oils such as castor oils, linseed oils, rapeseed oils,soybean oils and coconut oils; waxes such as tall oils, beeswaxes,carnauba waxes and lanolins; fatty acids and metal salts thereof such asricinolic acid, palmitic acid, stearic acid, 12-hydroxystearic acid,montanic acid, oleic acid and erucic acid; synthetic polymers such aspetroleum resins, coumarone-indene resins and atactic polypropylenes;ester plasticizers such as dioctyl phthalate, dioctyl adipate anddioctyl sebacate; microcrystalline waxes, liquid polybutadienes andmodified products or hydrogenated products thereof; and liquid Thiokols.

The crosslinking agents may be any of known crosslinking agents.Specific examples include organic peroxides such as dicumyl peroxide and2,5-dimethyl-2,5-tert-butylperoxyhexyne; sulfur; and morpholinedisulfide. The crosslinking agents may be used in combination withcrosslinking auxiliaries such as stearic acid and zinc oxide. Whensulfur is used, the amount thereof is preferably 0.1 to 10 parts byweight per 100 parts by weight of the olefin polymer. In the case of anorganic peroxide, the amount thereof is preferably 0.05 to 15 parts byweight per 100 parts by weight of the olefin polymer. In the case of aSiH group-containing compound, the amount thereof is usually 0.2 to 20parts by weight, preferably 0.5 to 10 parts by weight, and mostpreferably 0.5 to 5 parts by weight per 100 parts by weight of theolefin polymer. A SiH group-containing compound may be used togetherwith a catalyst, and a silane-coupling agent and/or a reaction inhibitoras an optional component.

[1-Butene polymers]

The novel 1-butene polymer of the invention has a meso pentad fraction(mmmm) as measured by ¹³C-NMR of 98.0% to 99.8%, preferably 98.5% to99.5%, and particularly preferably 99.0% to 99.4%.

The novel 1-butene polymer of the invention is substantially free fromregioirregular structures. The term “substantially” means that the totalof the proportion of regioerrors due to 2,1-insertions of 1-butenemonomers (hereinafter, also written as “2,1-insertion fraction”), andthe proportion of regioerrors due to 1,4-insertions (hereinafter, alsowritten as “1,4-insertion fraction”) in all the 1-butene constituentunits measured by ¹³C-NMR spectroscopy is not more than 0.1 mol %,preferably not more than 0.06 mol %, and particularly preferably belowthe detection limit.

Any mmmm that is below the lower limit or the presence of regioerrors inthe 1-butene polymer may cause insufficient heat resistance andrigidity. If the mmmm exceeds the upper limit, process-ability may bedeteriorated.

In the novel 1-butene polymer of the invention, the melting point Tmmeasured by differential scanning calorimetry (DSC) (heating rate: 10°C./min) is preferably 90 to 150° C., more preferably 100 to 140° C., andstill more preferably 120 to 140° C. With the melting point in thisrange, the 1-butene polymer achieves an excellent balance between heatresistance and process-ability.

The novel 1-butene polymer of the invention preferably has aweight-average molecular weight (Mw) and a molecular weight distribution(Mw/Mn) in the ranges described in [Olefin polymers]. The intrinsicviscosity [η] is preferably 0.1 to 10 dl/g, more preferably 0.3 to 5dl/g, and still more preferably 0.5 to 4 dl/g.

In the novel 1-butene polymer of the invention, it is preferable thatthe accumulated elution amount at a temperature [T_(X)] be 40% by weightor more relative to the whole elution amount as measured by crossfractionation chromatography (CFC) using o-dichlorobenzene as an eluent,provided that [T_(X)] is defined as ([T_(S)]+[T_(E)])/2 wherein [T_(S)]is an elution start temperature (a temperature at which the accumulatedelution weight percent reaches 0.5% by weight), and [T_(E)] is anelution end temperature (a temperature at which the accumulated elutionweight percent reaches 99% by weight). The accumulated elution amount ata temperature [T_(X)] is preferably 80% by weight or less, and morepreferably 70% by weight or less.

This indicator (the accumulated elution amount at [T_(X)]) indicatesthat the 1-butene polymer of the invention is eluted during CFCmeasurement in such a manner that the proportion of elution at lowertemperatures is relatively higher as compared to known 1-butenepolymers.

In general, 1-butene polymers with high stereoregularity have a thickcrystal phase and consequently the proportion of elution at highertemperatures during CFC measurement tends to be increased as compared tolow stereoregular 1-butene polymers. In contrast, the 1-butene polymerof the invention shows an inverse tendency. That is, the 1-butenepolymer of the invention is eluted during CFC measurement with arelatively larger proportion at lower temperatures in spite of the factthat the inventive 1-butene polymer has higher stereoregularity thanknown 1-butene polymers (see FIG. 1).

In general, highly stereoregular polymers have high yield stress becauseof a thick crystal phase, and consequently process-ability andstretching properties may be deteriorated at times. However, the1-butene polymer of the invention exhibiting a characteristic behaviorin CFC measurement has high tensile modulus due to its highstereoregularity while the yield stress thereof is of the same level asthat of known 1-butene polymers. Thus, it can be said that the 1-butenepolymer of the invention is a material having an excellentrigidity/yield stress balance.

Details of the measurements of these properties are described inExamples.

The novel 1-butene polymers of the invention substantially consist of1-butene-derived constituent units, but may include comonomer-derivedconstituent units without departing from the spirit of the invention.The term “substantially” means that the 1-butene polymers contain 95 wt% or more of 1-butene-derived constituent units. Examples of thecomonomers include the olefins described in [Olefin polymer productionprocesses].

For example, the 1-butene polymers having the aforementionedconfigurations and properties may be obtained by polymerizing 1-buteneand optionally a comonomer (for example, at least one olefin selectedfrom ethylene, propylene and a-olefins having 5 to 30 carbon atoms) inthe presence of the inventive olefin polymerization catalyst describedhereinabove. Detailed polymerization conditions are as described in[Olefin polymer production processes].

The 1-butene polymers of the invention having the aforementionedconfigurations and characteristics may be synthesized by, for example,the process described hereinabove, and are assumed to have a largeamount of a uniform and thin lamella structure. This lamella structureis probably the reason why the 1-butene polymers exhibit characteristicCFC measurement results.

After synthesized by the aforementioned process, the 1-butene polymersof the invention may be subjected to known post treatment steps such ascatalyst deactivation step, residual catalyst removal step and dryingstep as required.

The primary structure of the inventive 1-butene polymer is controlled tothe specific structure described above, and consequently the 1-butenepolymer exhibits high heat resistance and high mechanical propertiessuch as high rigidity and high strength. For example, the olefinpolymers of the invention have a higher melting point and a higherstereoregularity than conventional olefin polymers. Further, the1-butene polymers of the invention according to a preferred embodimenthave the specific accumulated elution amount at a temperature [T_(X)] asmeasured by CFC, and consequently exhibit an excellent rigidity/yieldstress balance.

With the properties described hereinabove (high heat resistance andrigidity/yield stress balance), the 1-butene polymers of the inventionwill be suitably used as materials for products such as pipes, films andsheets. In particular, pipes of the polymers will exhibit excellentthermal creep resistance.

[First 4-methyl-1-pentene polymers]

The first 4-methyl-1-pentene polymers of the invention fulfill thefollowing requirement (a) (constituent units), requirement (b)(stereoregularity) and requirement (c) (relationship between heat offusion ΔHm and melting point Tm).

<Requirement (a)>

In the first 4-methyl-1-pentene polymers of the invention, the amount ofconstituent units derived from 4-methyl-1-pentene is 100 to 80 mol %,preferably 100 to 90 mol %, and the amount of constituent units derivedfrom at least one selected from olefins having 2 to 30 carbon atoms(except 4-methyl-1-pentene) is 0 to 20 mol %, preferably 0 to 10 mol %.Hereinbelow, 4-methyl-1-pentene will be also written as “4MP1”, and the4-methyl-1-pentene polymers will be also written as “4MP1 polymers”.

Here, the total of the amount of constituent units derived from 4MP1 andthe amount of constituent units derived from at least one selected fromolefins having 2 to 30 carbon atoms (except 4MP1 monomer) is preferably100 mol %.

The olefins are preferably a-olefins. Examples of the olefins includethe olefins described in [Olefin polymer production processes].Preferred a-olefins are those having 2 to 20 carbon atoms (except 4MP1monomer). From the viewpoint of copolymerizability, more preferreda-olefins include ethylene, propylene, 1-butene, 1-hexene,3-methyl-1-butene, 3-methyl-1-pentene, 1-octene, 1-decene, 1-hexadecene,1-heptadecene and 1-octadecene, with propylene, 1-hexene, 1-octene,1-decene, 1-hexadecene and 1-octadecene being particularly preferable.

<Requirement (b)>

In the first 4-methyl-1-pentene polymers of the invention, the meso diadfraction (m) as measured by ¹³C-NMR is 98.5% to 100%. The fraction “m”is preferably 99% to 100%. Any fraction “m” that is less than the lowerlimit may result in insufficient heat resistance and rigidity.

<Requirement (c)>

In the first 4-methyl-1-pentene polymers of the invention, the heat offusion ΔHm (unit: J/g) and the melting point Tm (unit: ° C.) as measuredby differential scanning calorimetry (DSC) fulfill the followingrelation (1):

Relation (1): ΔHm≦0.5×Tm−76

Preferred ranges of ΔHm and Tm in the relation (1) are as follows.

In the first 4-methyl-1-pentene polymers of the invention, the meltingpoint Tm measured by differential scanning calorimetry (DSC) (heatingrate: 10° C./min) is preferably 100 to 260° C., more preferably 110 to250° C., still more preferably 150° C. to 250° C., further preferably152 to 250° C., particularly preferably 175 to 250° C., and mostpreferably 190 to 250° C.

In the first 4-methyl-1-pentene polymers of the invention, the heat offusion ΔHm measured by differential scanning calorimetry (DSC) (heatingrate: 10° C./min) is preferably 5 to 80 J/g, and more preferably 10 to60 J/g.

The relation (1) indicates that the first 4MP1 polymers of the inventionhave a higher heat of fusion than known 4MP1 polymers (see FIG. 3). Indetail, the first 4MP1 polymers of the invention have a higher heat offusion (ΔHm), namely, a higher degree of crystallinity than known 4MP1polymers when the polymers having approximately equal melting points(Tm) are compared. In view of the fact that the conventional 4MP1polymers exhibit a high melting point but usually have a small heat offusion, it can be said that the first 4MP1 polymers of the inventionachieve excellent properties.

The first 4MP1 polymers of the invention have excellent propertiesdescribed below. In usual crystalline polymers, an increase incrystallinity leads to an increase in rigidity such as tensile modulususually at the cost of a decrease in toughness such as elongation atbreak. In contrast, the first 4MP1 polymers of the invention satisfyingthe requirements (a) to (c), in particular, the relation (1) are freefrom a decrease in elongation at break in spite of having high tensilemodulus (see FIG. 2). This behavior is a very unusual characteristic forcrystalline polymers.

Details as to the establishment of the relation (1) are described inExamples.

The first 4MP1 polymers of the invention preferably have aweight-average molecular weight (Mw) and a molecular weight distribution(Mw/Mn) in the ranges described in [Olefin polymers]. The intrinsicviscosity [η] is preferably 0.1 to 20 dl/g, more preferably 0.2 to 10dl/g, and still more preferably 0.5 to 8 dl/g.

Details of the measurements of these properties are described inExamples.

For example, the first 4MP1 polymers having the aforementionedconfigurations and properties may be obtained by polymerizing 4MP1 andoptionally a comonomer (for example, at least one olefin selected fromα-olefins having 2 to 30 carbon atoms (except 4MP1)) in the presence ofthe inventive olefin polymerization catalyst described hereinabove.Detailed polymerization conditions are as described in [Olefin polymerproduction processes].

The first 4MP1 polymers of the invention having the aforementionedconfigurations and characteristics may be synthesized by, for example,the process described hereinabove. The characteristics of the first 4MP1polymers of the invention are probably manifested due to factors such asthe high stereoregularity of the 4MP1 polymers obtained by theaforementioned process and also the fact that the average length of 4MP1sequences in the polymers is shorter as compared to usual 4MP1 polymers.It is considered that this configuration results in a smaller thicknessand a smaller spherulite size of the crystalline lamella formed in thefirst 4MP1 polymers of the invention as compared to usual 4MP1 polymers.On the other hand, the first 4MP1 polymers of the invention have highcrystallinity due to the high stereoregularity.

Thus, the first 4MP1 polymers of the invention will compareadvantageously to usual 4MP1 polymers in that (1) the long period of thecrystal structure is short, and finer spherulites are formed in largeamounts, and (2) the crystalline lamella formed has a very uniformthickness and a very uniform spherulite size.

Based on the possible fact that the first 4MP1 polymers of the inventionhave the above characteristic crystal structure, the followingassumption is possible. In the case of usual 4MP1 polymers, even whenthe rigidity of the polymers is enhanced by the increase incrystallinity, the crystal structure size is nonuniform and consequentlythe polymer contains a mixture of portions which are highly or poorlyresistant to tensile deformation, with the result that a fracture occurseasily starting from, in particular, the portions which are poorlyresistant to tensile deformation. In contrast, the first 4MP1 polymersof the invention have little nonuniformity in crystal structure and arethus considered to exhibit uniform resistance to tensile deformationthroughout the structure, namely, have no portions which can serve asstarting points of fractures and are consequently prevented from adecrease in elongation at break.

With the properties described hereinabove (rigidity/toughness balance),the first 4MP1 polymers of the invention may be suitably used asmaterials for products such as films, sheets, tubes, injection moldedarticles, hollow molded articles and fibers. For example, the polymerswill be suitably used in applications such as materials for packagingfilms, release films, air-breathable films, reflective films, releasingpapers for synthetic leather, medical tubes, industrial tubes, foodcontainers, heat-resistant containers, medical containers, animal cages,physical and chemical science experimental equipment, mandrels for theproduction of rubber hoses, and nonwoven fabrics; as well as coatingmaterials, transparent modifiers, thermoplastic resin modifiers,modifiers for modifying properties such as releasing properties and gasbarrier properties of resins such as polyolefins, elastomers andrubbers, process-ability modifiers and compatibilizers (graftmodifiers).

The first 4MP1 polymers may be formed into fine powders by a crushingtreatment. For example, the thus-obtained fine powders maybe used asadditives in ink compositions or coating compositions, as additives inmetallurgic powder compositions, as additives in ceramic-sinteringpowder compositions, as additives in pressure-sensitive adhesives, asadditives in rubbers, as releasing agents in toners, and as moldreleasing agents. Further, the fine powders may be used as resinadditives in shaft bearings, gear wheels, cams, electric components,camera components, automobile components and household articlecomponents, or as resin additives in products such as waxes, greases,engine oils, fine ceramics and platings.

[Second 4-methyl-1-pentene polymers]

The second 4-methyl-1-pentene polymers of the invention fulfill thefollowing requirement (d) (constituent units), requirement (e)(stereoregularity) and requirement (f) (melting point Tm).

<Requirement (d)>

In the second 4-methyl-1-pentene polymers of the invention, the amountof constituent units derived from 4-methyl-1-pentene is more than 50 mol% and less than 80 mol %, and the amount of constituent units derivedfrom at least one selected from olefins having 2 to 30 carbon atoms(except 4-methyl-1-pentene) is more than 20 mol % and less than 50 mol%. The amount of constituent units derived from. 4MP1 is preferably morethan 50 mol % and less than 78 mol %, and the amount of constituentunits derived from the olefin(s) ispreferably more than 22 mol % andless than 50 mol %.

Here, the total of the amount of constituent units derived from 4MP1 andthe amount of constituent units derived from at least one selected fromolefins having 2 to 30 carbon atoms (except 4MP1) is preferably 100 mol%.

The olefins are preferably α-olefins. Examples of the olefins includethe olefins described in [Olefin polymer production processes].Preferred a-olefins are those having 2 to 20 carbon atoms (except 4MP1monomer). From the viewpoint of copolymerizability, more preferreda-olefins include ethylene, propylene, 1-butene, 1-hexene,3-methyl-1-butene, 3-methyl-1-pentene, 1-octene, 1-decene, 1-hexadecene,1-heptadecene and 1-octadecene, with ethylene, propylene and 1-butenebeing particularly preferable.

<Requirement (e)>

In the second 4-methyl-1-pentene polymers of the invention, the mesodiad fraction (m) as measured by ¹³C-NMR is 98.5% to 100%. The fraction“m” is preferably 99% to 100%. Any fraction “m” that is less than thelower limit may result in insufficient mechanical properties such aspermanent compression set.

<Requirement (f)>

In the second 4-methyl-1-pentene polymers of the invention, the meltingpoint Tm as measured by differential scanning calorimetry (DSC) (heatingrate: 10° C./min) is lower than 100° C. or is substantially absent.Here, the phrase “the melting point is substantially absent” means thatthe heat of fusion ΔHm (unit: J/g) is not substantially observed duringdifferential scanning calorimetry (DSC) (heating rate: 10° C./min). Thephrase “the heat of fusion ΔHm is not substantially observed” means thatΔHm is less than 5 J/g, preferably 1 J/g or below, and more preferablybelow the detection limit (=approximately 0.1 J/g). Thus, the second4-methyl-1-pentene polymers of the invention are amorphous orlow-crystalline polymers.

The second 4MP1 polymers of the invention preferably have aweight-average molecular weight (Mw) and a molecular weight distribution(Mw/Mn) in the ranges described in [Olefin polymers]. The intrinsicviscosity [η] is preferably 0.1 to 20 dl/g, more preferably 0.2 to 10dl/g, and still more preferably 0.5 to 8 dl/g.

(Gel fraction) The second 4MP1 polymers of the invention preferably havea gel fraction measured by extraction with boiling p-xylene (solvent) inthe range of 0 to 10 wt %, more preferably 0 to 5 wt %, and particularlypreferably 0 to 0.5 wt %. The polymers exhibit excellent elasticproperties in spite of such a low gel fraction.

Details of the measurements of these properties are described inExamples.

The second 4MP1 polymers of the invention satisfying the requirements(d) to (f) are characterized in that the loss tangent (tanδ) measuredwith respect to dynamic viscoelasticity is higher while the polymers donot show a decrease in permanent compression set that is an indicator ofelastic properties as compared to known amorphous or low-crystalline4MP1 polymers having a similar 4MP1 content.

It is generally known that when the loss tangent (tanδ=G″/G′) is high,viscous properties (G″) are manifested more strongly than elasticproperties (G′) to cause a decrease in elastic properties such aspermanent compression set. In contrast, there is no decrease in thepermanent compression set of the second 4MP1 polymers of the inventionin spite of the high loss tangent.

For example, the second 4MP1 polymers having the aforementionedconfigurations and properties may be obtained by polymerizing 4MP1 andoptionally a comonomer (for example, at least one olefin selected fromα-olefins having 2 to 30 carbon atoms (except 4MP1)) in the presence ofthe inventive olefin polymerization catalyst described hereinabove.Detailed polymerization conditions are as described in [Olefin polymerproduction processes].

The second 4MP1 polymers of the invention having the aforementionedconfigurations and characteristics may be synthesized by, for example,the process described hereinabove. The present inventors assume that theabove characteristics of the second 4MP1 polymers of the invention areattributed to the following reasons.

The viscous properties (G″) are predominantly governed by the magnitudeof frictional force between molecular chains which depends on theprimary structure (monomers). In 4MP1 polymers, this factor is dependentonly on the copolymerization composition and will not significantlydiffer between the second 4MP1 polymers of the invention and usual 4MP1polymers provided that the 4MP1 contents are similar.

On the other hand, the second 4MP1 polymers of the invention exhibit asmaller permanent compression set, namely, are excellent in strainrecovery. The reason for this may be considered as follows. In 4MP1polymers, it is known that even non-crystalline or amorphous regionscontain spatially-ordered aggregated structures having sizes ofapproximately several hundreds of nanometers. The formation of suchaggregated structures is considered to be because of the low mobility ofmolecules due to the rigidity of 4MP1 polymer chains (the rigidity beingascribed to the bulkiness of side chains).

In usual 4MP1 polymers, it is probable that such aggregated structurespresent in amorphous regions have nonuniform sizes and have smallproportions. In contrast, the second 4MP1 polymers of the invention areprobably such that amorphous regions contain uniformly-sized aggregatedstructures in large proportions. The reason for this assumption isbecause the second 4MP1 polymers of the invention have structures thatare highly stereoregular and are easily aggregated even in the casewhere the polymers are amorphous.

Such aggregated structures in amorphous regions are considered to serveas “pseudo crosslinks” resistant to external deformations such ascompression and tension. Thus, increasing the proportion of pseudocrosslinks will increase the amount of recovery from deformation whenthe stress such as compression is released. This is probably the reasonwhy the second 4MP1 polymers of the invention do not show a decrease inpermanent compression set in spite of the fact that the polymers have ahigh tanδ.

With the viscoelastic properties described hereinabove, the second 4MP1polymers of the invention may be suitably used as materials for productssuch as vibration damping materials, vibration insulating materials,soundproof materials, impact absorbers and sound insulators in the formsof films, sheets and injection molded articles. For example, thepolymers will be suitably used in applications such as vibrationinsulating mats, vibration insulating dampers and interior materials instructures such as audio equipment, OA devices, industrial machinery,automobiles, railways, bridges and ships; vibration damping materials,vibration insulating materials, soundproof materials and soundinsulators in devices such as home electric appliances, for example, airconditioners and washing machines; impact absorbers such as mouthguards, sport protectors, nursing protectors, mats and inner shoe soles;pressure-sensitive adhesives such as pressure-sensitive adhesive filmsand pressure-sensitive adhesive layers in protective films; protectivefilms in semiconductor manufacturing steps; gripes in products such assport gears, stationery and health items; modifiers for polyolefins suchas polypropylene, poly-4-methyl-1-pentene, polybutene and polyethylene,elastomer modifiers, rubber modifiers, acrylic pressure-sensitiveadhesive modifiers, hot melt adhesive modifiers, forming modifiers suchas flow mark inhibitors, weld modifiers and surface modifiers, resinmodifiers such as gas barrier modifiers and release modifiers, andcompatibilizers (such as graft modifiers).

The second 4MP1 polymers may be formed into fine powders by a crushingtreatment. For example, the thus-obtained fine powders maybe used asadditives in ink compositions or coating compositions such as vibrationdamping coatings, as additives in metallurgic powder compositions, asadditives in ceramic-sintering powder compositions, and as additives inpressure-sensitive adhesives.

[Shaped Articles]

The shaped articles of the invention include the olefin polymers, or the1-butene polymers or the 4-methyl-1-pentene polymers described above.These olefin polymers maybe shaped into desired articles such as films,sheets, hollow molded articles, injection molded articles and fibers byvarious shaping methods such as injection molding, extrusion, injectionstretch blow molding, blow molding, casting, calendering, press molding,stamping, blown-film extrusion and rolling.

Examples of the applications of the shaped articles of the invention aredescribed below. However, the applications are not particularly limitedthereto.

Examples of containers include food containers, retort containers andbottle containers such as eating utensils, seasoning containers, retortcontainers, freeze preservation containers, retort pouches, microwavableheat-resistant containers, frozen food containers, frozen dessert cups,cups, baby feeding bottles and beverage bottles; blood transfusion sets,medical bottles, medical containers, medical hollow bottles, medicalbags, transfusion bags, blood preservation bags, transfusion bottlechemical containers, detergent containers, softener agent containers,bleaching agent containers, shampoo containers, conditioner containers,cosmetic containers, perfume containers, toner containers, powdercontainers, adhesive containers, gasoline tank containers and kerosinecontainers.

Examples of packaging materials include food packaging materials, meatpackaging materials, processed fish packaging materials, vegetablepackaging materials, fruit packaging materials, fermented food packagingmaterials, sweets packaging materials, oxygen absorbent packagingmaterials, retort food packaging materials, freshness preservationfilms, drug packaging materials, cell culture bags, cell inspectionfilms, bulb packaging materials, seed packaging materials,vegetable/fungus cultivation films, heat-resistant vacuum moldedcontainers, prepared food containers, prepared food container lids,industrial wrapping films, household wrapping films and baking cartons.

Examples of films, sheets and tapes include:

releasing films such as releasing films for flexible printed boards,releasing films for ACM boards, releasing films for rigid boards,releasing films for rigid flexible boards, releasing films for advancedcomposite materials, releasing films for the curing of carbon fibercomposite materials, releasing films for the curing of glass fibercomposite materials, releasing films for the curing of aramid fibercomposite materials, releasing films for the curing of nano compositematerials, releasing films for the curing of fillers, releasing filmsfor the sealing of semiconductors, releasing films for polarizingplates, releasing films for diffusion sheets, releasing films for prismsheets, releasing films for reflective sheets, cushion films forreleasing films, releasing films for fuel cells, releasing films forvarious rubber sheets, releasing films for the curing of urethanes, andreleasing films for the curing of epoxies,

solar battery cell sealing sheets, solar battery cell back sheets,plastic films for solar batteries, battery separators, separators forlithium ion batteries, electrolyte membranes for fuel cells,pressure-sensitive adhesive/adhesive separators, light guide plates,optical disks,

substrates, pressure-sensitive adhesives and separators forsemiconductor processing films such as dicing tapes, back grind tapes,die bonding films, two-layer FCCLs and films for film capacitors;pressure-sensitive adhesive films, stress releasing films, films forpellicles, films for polarizing plates; protective films such aspolarizing plate protective films, liquid crystal panel protectivefilms, optical component protective films, lens protective films,electric component/electric device protective films, mobile phoneprotective films, personal computer protective films, touch panelprotective films, window glass protective films, films for baked paints,masking films, films for capacitors, capacitor films, films for fuelcell capacitors, reflective films, diffusion films, laminates (includingglass), radiation resistant films, γ-ray resistant films, and porousfilms;

heat release films/sheets, frames for the manufacturing of electroniccomponent sealants, LED molds, laminate plates for high-frequencycircuits, high-frequency cable coating materials, optical waveguidesubstrates, glass fiber composites, carbon fiber composites,

glass interlayer films, laminated glass films, building window films,bulletproof materials, bulletproof glass films, heat shield sheets, heatshield films,

releasing papers such as releasing papers for synthetic leather,releasing papers for advanced composite materials, releasing papers forthe curing of carbon fiber composite materials, releasing papers for thecuring of glass fiber composite materials, releasing papers for thecuring of aramid fiber composite materials, releasing papers for thecuring of nano composite materials, and releasing papers for the curingof fillers; and heat-resistant waterproof printing papers.

Examples of other applications include:

mandrels for the production of rubber hoses, sheaths, sheaths for theproduction of rubber hoses, hoses, tubes, cooling-water pipes, hot-waterpipes, wire coating materials, millimeter-wave signal cable coatingmaterials, high-frequency signal cable coating materials, eco wirecoating materials, vehicle cable coating materials, signal cable coatingmaterials, insulators for high-voltage wires, wiring ducts, tubes forcosmetics and perfume sprays, medical tubes, transfusion tubes, pipes,wire harnesses,

interior and exterior materials for structures such as automobiles,motorcycles, railroad vehicles, air planes and ships; abrasion-resistantautomotive interior and exterior materials, instrument panel skins, doortrim skins, rear package trim skins, ceiling skins, rear pillar skins,seat back garnishes, console boxes, arm rests, air bag case lids, shiftknobs, assist gripes, side step mats, reclining covers, sheets intrunks, seat belt buckles; moldings such as inner/outer moldings, bumpermoldings, side moldings, roof moldings and belt moldings; air spoilers;automotive seal materials such as door seals and body seals; automotiveinterior and exterior materials such as glass run channels, mudguards,kicking plates, step mats, number plate housings, automotive hosecomponents, air duct hoses, air duct covers, air intake pipes, air damskirts, timing belt cover seals, bonnet cushions, door cushions, cupholders, side break gripes, shift knob covers, seat adjustment knobs,wire harness grommets, suspension cover boots, glass guides, inner beltline seals, roof guides, trunk lid seals, molded quarter window gaskets,corner moldings, glass encapsulations, hood seals, glass run channels,secondary seals, bumper components, body panels, side shields, doorskins, weather strip materials, hoses, steering wheels, wire harnesscovers and seat adjuster covers; special tires such as vibration dampingtires, silent tires, car race tires and radio control tires; packings,automotive dust covers, lamp seals, automotive boots, rack and pinionboots, timing belts, wire harnesses, grommets, emblems, air filterpackings, automotive connectors, ignition coils, switches, lampreflectors, relays, electric control unit cases, sensor housings,electromagnetic valves, coil sealing components,

skin materials for products such as furniture, shoes, garments, bags andbuilding materials; building seal materials, waterproof sheets, buildingmaterial sheets, building material gaskets, building material windowfilms, iron-core protecting components, soil improvement sheets, waterstop materials, joint materials, gaskets, doors, door frames, windowframes, cornices, baseboards, open frames, floor materials, ceilingmaterials, wall papers,

health items (e.g., nonslip mats/sheets and fall preventionfilms/mats/sheets), health appliance components, impact absorbing pads,protectors/protecting components (e.g., helmets and guards), sport gears(e.g., sport gripes and protectors), sport protecting equipment,rackets, mouth guards, balls, golf balls, haulage gears (e.g., haulageimpact absorbing gripes and impact absorbing sheets), vibration dampingpallets; impact absorbers such as impact absorbing dampers, insulators,impact absorbers for shoes, impact absorbing foams and impact absorbingfilms/sheets;

gripes (such as stationery, tools, sporting equipment, steering wheels,commodities, electric devices and furniture), sundries, toys, treads,shoe soles, shoe midsoles/inner soles, soles, sandals, chair skins,bags, school bags; garments such as jackets and coats; belts, sashes,ribbons, notebook covers, book covers, key chains, pencil cases,wallets, business card holders, commuter-pass holders, suckers, toothbrushes, floor materials, gymnastic mats, electrical tool components,agricultural equipment components, heat dissipation materials,transparent substrates, soundproof materials, cushion materials, wirecables, shape memory materials, connectors, switches, plugs, homeappliance components (such as motor components and housings),

medical gaskets, medical caps, drug caps, gaskets; packing materialsused in high-temperature treatments such as boiling and high-pressuresteam sterilization after the filling of bottles with items such as babyfood, dairy products, drugs and sterilized water; industrial sealmaterials, industrial sewing machine tables, number plate housings; capliners such as PET bottle cap liners;

pressure-sensitive adhesives such as protect film pressure-sensitiveadhesive layers and hot melt pressure-sensitive adhesives;

stationery, office supplies; supporting members of precision devices andOA devices such as OA printer legs, facsimile legs, sewing machine legs,motor supporting mats and audio vibration-insulating materials;heat-resistant packings for office automation, animal cages; physicaland chemical science experimental equipment such as beakers andmeasuring cylinders; medical films/sheets, cell culture films/sheets,syringes, cells for optical measurements, garment cases, clear cases,clear files, clear sheets, desk mats, and

fibers such as monofilaments, multifilaments, cut fibers, hollow fibers,nonwoven fabrics, stretchable nonwoven fabrics, fibers, waterprooffabrics, air-breathable woven fabrics and fabrics, disposable diapers,sanitary products, hygiene products, filters, bug filters,dust-collecting filters, air cleaners, hollow fiber filters,water-purifying filters, filter fabrics, filter papers and gasseparation membranes.

Examples of other suitable applications include coating materials, filmsand sheets obtained by coating, release materials, water repellants,insulating films, adhesives, pressure-sensitive adhesives, coatedpapers, transparent sealants, sealants, hot melt pressure-sensitiveadhesives, solvent-based pressure-sensitive adhesives,pressure-sensitive adhesive films, fabric tapes, craft tapes and elasticadhesives.

EXAMPLES

The present invention will be described in further detail based onExamples hereinbelow. However, the scope of the invention is not limitedto such Examples.

[Property Measurement Methods] Intrinsic Viscosity ([η])

With automated kinetic viscometer VMR-053PC and a modified Ubbelohdecapillary viscometer manufactured by RIGO CO., LTD., the specificviscosity lisp at 135° C. in decalin was measured. The intrinsicviscosity ([η]) was calculated using the following equation.

[η]=ηsp/{C(1+K·ηsp)}(C: solution concentration [g/dl], K: constant)

Weight-Average Molecular Weight (Mw) and Number-Average Molecular Weight(Mn)

With Alliance GPC 2000 manufactured by Waters, 500 μl of a 0.15 (w/v)%sample solution was pumped at a flow rate of 1.0 ml/min to measure theweight-average molecular weight (Mw) and the number-average molecularweight (Mn). Standard polystyrenes manufactured by TOSO CORPORATION wereused. The molecular weights were calculated relative to thepolystyrenes.

Separation columns: two TSKgel GMH6-HT columns and two TSKgel GMH6-HTLcolumns (each 7.5 mm in inner diameter and 300 mm in length)

Column temperature: 140° C.

Mobile phase: o-dichlorobenzene

-   -   (containing 0.025 wt % dibutylhydroxytoluene)

Detector: differential refractometer

-   Melting point (Tm), crystallization temperature (Tc), heat of fusion    (ΔHm) and CFC analysis-   (Melting point and crystallization temperature of butene    homopolymers obtained by normal-pressure polymerization)

With RDC220 manufactured by Seiko Instruments Inc., approximately 5 mgof a sample was heated from 30° C. to 200° C. in a nitrogen atmosphere(50 mL/min). The sample was held at 200° C. for 5 minutes and was cooledto −50° C. at 10° C./min. After being held at −50° C. for 5 minutes, thesample was heated to 200° C. at 10° C./min. The top of thecrystallization peak observed during the cooling was obtained as thecrystallization temperature (Tc), and the top of the crystal fusion peakobserved during the second heating was obtained as the melting point(TmII).

The sample analyzed as described above was allowed to stand at least for10 days at 23° C., and was heated from room temperature, specifically,30° C. to 200° C. at 10° C./min. The top of the crystal fusion peakobserved during the heating was obtained as the melting point (Tm).

<Melting Point and Crystallization Temperature of Butene HomopolymersObtained by Pressure Polymerization>

With EXSTAR DSC6220 manufactured by SII Nano Technology, approximately 4mg of a sample was heated from 30° C. to 200° C. in a nitrogenatmosphere (30 mL/min). The sample was held at 200° C. for 5 minutes andwas cooled to −50° C. at 20° C./min. After being held at −50° C. for 5minutes, the sample was heated to 200° C. at 10° C./min.

The sample was allowed to stand at room temperature (20 to 25° C.) forat least 10 days, and was heated from 30° C. to 200° C. at 10° C./min.The sample was then held at 200° C. for 5 minutes and was cooled to 30°C. at 20° C./min. The top of the crystallization peak observed duringthe cooling was obtained as the crystallization temperature (Tc), andthe top of the crystal fusion peak observed during the heating wasobtained as the melting point (Tm).

<Cross Fractionation Chromatography (CFC)>

The following apparatus was used in the measurement.

Apparatus: cross fractionation chromatograph CFC2 (manufactured byPolymer Char)

Detector: infrared band pass filter detector IR4 (manufactured byPolymer Char)

Wavelength detection range: approximately 3000 to 2800 cm¹

TREF column: stainless steel column (⅜ inch in outer diameter×15 cm inlength, included in the apparatus)

GPC columns: Shodex HT-806M×3 (manufactured by SHOWA DENKO K.K.)

Molecular weight: polystyrene-equivalent molecular weight relative tomonodispersed polystyrenes (manufactured by TOSO CORPORATION)

Eluent: o-dichlorobenzene (special grade, manufactured by Wako PureChemical Industries, Ltd.)

Flow rate: 1.0 mL/min

Amount of sample injection: 0.5 mL

GPC column temperature: 140° C.

A sample prepared under the conditions described later was injected intothe CFC apparatus, and was held in the TREF column at 145° C. for 10minutes and at 140° C. for 20 minutes. Thereafter, the sample was cooledto −20° C. at 1° C./min, and was allowed to stand for 60 minutes.Thereafter, the TREF column was heated in accordance with the elutionfractions described later. Components that were eluted during eachheating operation were transferred to the GPC columns, and the molecularweight distribution and the elution amount were determined. Theaccumulated elution amount at a temperature [T_(X)] relative to thewhole elution amount was measured. [T_(X)] was defined as([T_(S)]+[T_(E)])/2 wherein [T_(S)] was an elution start temperature (atemperature at which the accumulated elution weight percent reached 0.5%by weight) , and [T_(E)] was an elution end temperature (a temperatureat which the accumulated elution weight percent reached 99% by weight) .When [T_(X)] did not agree with the elution fraction temperature, theaccumulated elution amount at [T_(X)] was obtained by assuming that theaccumulated elution amount would have been increased linearly betweenthe accumulated elution amounts at the immediately adjacent elutionfraction temperatures below and above [T_(X].)

<Sample Preparation Conditions>

Sample concentration: 120 mg/30 mL

Solvent used in sample preparation: o-dichlorobenzene (special grade,manufactured by Wako Pure Chemical Industries, Ltd.)

Sample preparation temperature: 145° C. Elution fractions: −20, 0, 2, 4,6, 8, 10, 12, 14, 16, 18, 20, 22, 24, 26, 28, 30, 32, 34, 36, 38, 40,42, 44, 46, 48, 50, 52, 54, 56, 58, 60, 62, 64, 66, 68, 70 and 140° C.(38 fractions in total)

<Melting Point, Crystallization Temperature and Heat of Fusion of4-methyl-1-pentene homopolymers>

With EXSTAR DSC7020 manufactured by SII Nano Technology, approximately 5mg of a sample was heated from 30° C. to 300° C. in a nitrogenatmosphere (30 mL/min). The sample was held at 300° C. for 5 minutes andwas cooled to 0° C. at 10° C./min. After being held at 0° C. for 5minutes, the sample was heated to 300° C. at 10° C./min. The top of thecrystallization peak observed during the cooling was obtained as thecrystallization temperature (Tc), and the top of the crystal fusion peakobserved during the second heating was obtained as the melting point(Tm). The heat of fusion ΔHm was calculated by integrating the crystalfusion peak.

<Melting Point, Crystallization Temperature and Heat of Fusion of4-methyl-1-pentene/propylene copolymers>

With EXSTAR DSC7020 manufactured by SII Nano Technology, approximately 5mg of a sample was heated from 30° C. to 250° C. in a nitrogenatmosphere (30 mL/min). The sample was held at 250° C. for 5 minutes andwas cooled to 0° C. at 10° C./min. After being held at 0° C. for 5minutes, the sample was heated to 250° C. at 10° C./min. The top of thecrystallization peak observed during the cooling was obtained as thecrystallization temperature (Tc), and the top of the crystal fusion peakobserved during the second heating was obtained as the melting point(Tm). The heat of fusion ΔHm was calculated by integrating the crystalfusion peak.

<Melting Point, Crystallization Temperature and Heat of Fusion of4-methyl-1-pentene1-octene copolymers, 4-methyl-1-pentene1-decenecopolymers and 4-methyl-1-pentene1-hexadecene1-octadecene copolymers)

With EXSTAR DSC6220 manufactured by SII Nano Technology, approximately 4mg of a sample was heated from 30° C. to 280° C. in a nitrogenatmosphere (30 mL/min). The sample was held at 280° C. for 5 minutes andwas cooled to −50° C. at 10° C./min. After being held at −50° C. for 5minutes, the sample was heated to 280° C. at 10° C./min. The top of thecrystallization peak observed during the cooling was obtained as thecrystallization temperature (Tc), and the top of the crystal fusion peakobserved during the second heating was obtained as the melting point(Tm). The heat of fusion ΔHm was calculated by integrating the crystalfusion peak.

Stereoregularity (mmmm and Regioirregularity) of Polybutenes

The meso pentad fraction (mmmm), and the regioirregularity due to2,1-insertions and 1,4-insertions were calculated by ¹³C-NMRspectroscopy. In the ¹³C-NMR spectroscopy, 50 mg of a sample wasdissolved in 0.6 ml of a 4/1 mixture solvent including o-dichlorobenzeneand deuterated benzene (o-dichlorobenzene/deuterated benzene by volume),and the solution was analyzed on nuclear magnetic resonance apparatusAVANCE III cryo-500 manufactured by Bruker BioSpin K.K. under conditionsof 120° C., 45° pulse, 5.5 sec repetition time and 256 scans. Thereference chemical shift was 27.50 ppm assigned to the mmmm of theside-chain methylene groups. The peaks were assigned with reference toK. Matsuzaki, T. Uryu, T. Asakura, NMR SPECTROSCOPY AND STEREOREGULARITYOF POLYMERS, JAPAN SCIENTIFIC SOCIETIES PRESS.

In the measurement, the peaks assigned to mmmm and mmmr, and the peaksassigned to rmmr and mmrr were not separate from each othersufficiently. Thus, the meso pentad fraction (mmmm): F (mmmm)×100 (%)was calculated using the following equation assuming that I (mmmr)=I(mmrr)+I (mrrm) and I (rmmr)=0.

F (mmmm)=[I (mmmm+mmmr)−I (rmmr+mmrr)−I (mrrm)]/I (CH2)

I (X) indicates the integral of a methylene peak at 26.2 to 28.5 ppmassigned to X. I (CH₂) indicates the total area of methylene peaks at26.2 to 28.5 ppm. The detection limit was 0.01%.

Propylene content in 4-methyl-1-pentene/propylene copolymers, andα-olefin content in 4-methyl-1-pentene/α-olefin copolymers

The propylene content in 4-methyl-1-pentene/propylene copolymers, andthe α-olefin content in 4-methyl-1-pentene/α-olefin copolymers werecalculated by ¹³C-NMR spectroscopy using the following apparatus andconditions.

The nuclear magnetic resonance apparatus was AVANCE III cryo-500manufactured by Bruker BioSpin K. K. The solvent was ano-dichlorobenzene/benzene-d₆ (4/1 v/v) mixed solvent. The sampleconcentration was 55 mg/0.6 mL. The measurement temperature was 120° C.The nucleus observed was ¹³C (125 MHz). The sequence was single pulseproton broad band decoupling. The pulse width was 5.0 μsec (45° pulse).The repetition time was 5.5 sec. The number of scans was 64. Thereference chemical shift was 128 ppm of benzene-d₆. The main-chainmethine signal was integrated, and the propylene content was calculatedusing the following equation.

Propylene content (%)=[P/(P+M)]×100

Here, P indicates the total peak area of signals assigned to methine inthe propylene main chain, and M indicates the total peak area of signalsassigned to methine in the 4-methyl-1-pentene main chain.

With respect to 4-methyl-1-pentene/α-olefin copolymers, the signalsassigned to α-olefins (except 4MP1) were integrated, and the α-olefincontents were calculated in the similar manner.

Iso Diad Tacticity of 4-methyl-1-pentene polymers

The iso diad tacticity (meso diad fraction) of 4-methyl-1-pentenepolymers was defined as the proportion of head-to-tail coupled diad4-methyl-1-pentene unit sequences in which the isobutyl branches were onthe same side of the polymer chain shown as a planar zigzag structure.This tacticity was obtained by ¹³C-NMR spectroscopy using the followingequation.

Iso diad tacticity (%)=[m/(m+r)]×100

[In the equation, m and r indicate absorption intensities assigned tothe main-chain methylene groups in head-to-tail coupled4-methyl-1-pentene units illustrated below:

In the ¹³C-NMR spectroscopy, the nuclear magnetic resonance apparatuswas AVANCE III cryo-500 manufactured by Bruker BioSpin K. K. The solventwas an o-dichlorobenzene/benzene-d₆ (4/1 v/v) mixed solvent. The sampleconcentration was 60 mg/0.6 mL. The measurement temperature was 120° C.The nucleus observed was ¹³C (125MHz). The sequence was single pulseproton broad band decoupling. The pulse width was 5.0 μsec (45° pulse).The repetition time was 5.5 sec. The reference chemical shift was 128ppm of benzene-d₆.

The peak region in the range of 41.5 to 43.3 ppm was divided at theminimum of the peak profile into a first region on the higher magneticfield side and a second region on the lower magnetic field side.

The resonance peak in the first region was assigned to the main-chainmethylene in diad 4-methyl-1-pentene unit sequences illustrated in (m).This peak was regarded as representing a 4-methyl-1-pentene homopolymer,and its integral was obtained as “m”. The resonance peak in the secondregion was assigned to the main-chain methylene in diad4-methyl-1-pentene unit sequences illustrated in (r), and its integralwas obtained as “r”. The detection limit was 0.01%.

Soluble Proportion (SP) in 4-methyl-1-pentene homopolymers

A polymer slurry was separated by filtration into a solid polymer (awhite solid) and a filtrate. The solvent of the filtrate was evaporated,and thereby the polymer that had been dissolved in the filtrate wasobtained. The proportion of the polymer that had been dissolved in thefiltrate was calculated using the following equation.

Proportion of polymer in filtrate (wt %)=W2/(W1+W2)×100

W1: mass (g) of solid polymer (white solid) filtered

W2: mass (g) of polymer dissolved in filtrate of slurry

Gel Fraction in 4-methyl-1-pentene polymers

To determine the gel fraction, approximately 5 g of a sample was placedinto a No. 325 mesh metal thimble of a Soxhlet extractor, and wasextracted for 3 hours while boiling and refluxing p-xylene. The residuein the metal thimble was weighed, and the gel fraction was calculatedusing the following equation.

Gel fraction (%)=(weight of residue [g]/initial weight [g])×100

Identification of Structures and Purities of Compounds and Catalysts

The structures and purities of compounds and catalysts obtained inExamples and other studies were determined by methods such as nuclearmagnetic resonance (NMR, GSH-270 manufactured by JEOL Ltd.) , fielddesorption mass spectrometry (FD-MS, SX-102A manufactured by JEOL Ltd.)and gas chromatography mass spectrometry (GC-MS, HP6890/HP5973manufactured by Hewlett-Packard or GC-17A/GCMS-QP5050A manufactured byShimadzu Corporation). The steric structures of metallocene compoundswere determined by comparing a spectrum obtained by ¹H-NMR measurementto theoretical spectra calculated with respect to various stereoisomers.

Unless otherwise mentioned, all examples were carried out in a drynitrogen atmosphere using a dried solvent.

1,1,4,4,7,7,10,10-Octamethyl-2,3,4,7,8,9,10,12-octahydro-1H-dibenzo[b,h]fluorenewas synthesized in accordance with Examples described in WO 2001/27124.Hereinbelow, 1,1,4,4,7,7,10,10-octamethyl-2,3,4,7,8,9,10,12-octahydro-1H-dibenzo[b,h]fluorene will be written as “octamethylfluorene”.

[Synthesis of Transition Metal Compounds]

[Synthetic Example 1] Synthesis of(1-octamethylfluoren-12′-yl-5-tert-butyl-3-isopropyl-1-methyl-1,2,3,4-tetrahydropentalene)zirconiumdichloride (catalyst A)

(1) 5-Tert-butyl-1-isopropyl-3-methyl-1,2-dihydropentalene: In anitrogen atmosphere, a 100 ml three-necked flask was loaded with 50 mlof methanol, 2.54 g of tert-butylcyclopentadiene, 5.2 ml of pyrrolidineand 2.1 ml of isobutyl aldehyde in an ice water bath. The mixture wasstirred at room temperature for 4 hours and at 40° C. for 1.5 hours.After the addition of 2.1 ml of additional isobutyl aldehyde, themixture was stirred at room temperature for 18 hours and at 70° C. for 7hours. 7.0 ml of acetone was added, and reaction was performed at 70° C.for 17 hours. Further, 10 ml of acetone was added, and the mixture wasstirred at 70° C. for 6 hours. The reaction solution was poured into 150ml of 0.5 M hydrochloric acid. The organic layer was separated. Theaqueous layer was extracted with 150 ml of hexane. The obtained extractwas combined with the previously separated organic layer, and thecombined organic layer was washed with a saturated aqueous sodiumhydrogen carbonate solution, water and a brine. The liquid was driedwith magnesium sulfate, and the solvent was evaporated. The residue waspurified by column chromatography to afford the title compound. Theamount obtained was 0.96 g, and the yield was 21%.

(2)1-Octamethylfluoren-12′-yl-5-tert-butyl-3-isopropyl-1-methyl-1,2,3,4-tetrahydropentalene:In a nitrogen atmosphere, a 100 ml three-necked flask was loaded with1.54 g of octamethylfluorene and 30 ml of tert-butyl methyl ether. In anice water bath, 2.60 ml of a 1.59 M hexane solution of n-butyllithiumwas added dropwise over a period of 12 minutes. The mixture was stirredat room temperature for 2 hours and at 40° C. for 2 hours. 15 ml of atert-butyl methyl ether solution of 0.96 g of5-tert-butyl-1-isopropyl-3-methyl-1,2-dihydropentalene was added at −12°C. over a period of 30 minutes. The mixture was stirred at roomtemperature for 21 hours. The resultant reaction solution was added to100 ml of 0.1 N hydrochloric acid. The organic layer was separated. Theaqueous layer was extracted with 80 ml of hexane. The obtained extractwas combined with the previously separated organic layer, and thecombined organic layer was washed one time with a saturated aqueoussodium hydrogen carbonate solution, two times with water, and one timewith a brine. The liquid was dried with magnesium sulfate, and thesolvent was evaporated. The resultant solid was washed with methanol toafford the title compound. The amount obtained was 1.48 g, and the yieldwas 62%.

The compound was identified to be the target compound based on theresults of the FD-MS measurement. FD-MS: m/Z=602.5 (Mt).

¹H-NMR showed that the compound was a mixture of isomers.

(3) Catalyst A: In a nitrogen atmosphere, a 30 ml Schlenk flask wasloaded with 0.699 g of1-(octamethylfluoren-12′-yl)-5-tert-butyl-3-isopropyl-1-methyl-1,2,3,4-tetrahydropentalene,0.140 g of a-methylstyrene, 10 g of hexane, and 1.15 ml of cyclopentylmethyl ether. In an oil bath at 26° C., 1.45 ml of a 1.65 M hexanesolution of n-butyllithium was added dropwise over a period of 15minutes. The mixture was stirred at 70° C. for 4 hours and was cooled inan ice/acetone bath. The liquid was degassed by evacuating the systemfor 5 minutes, and the pressure was returned to normal pressure withnitrogen. After the addition of 0.293 g of zirconium tetrachloride,reaction was performed for 17.5 hours while gradually returning thetemperature to room temperature.

The solvent was evaporated, and soluble components were extracted withhexane. The insolubles were removed by filtration, and the insolubleswere washed with hexane. The solution obtained was concentrated and wasrecrystallized in hexane. The solid was filtered and was dried underreduced pressure to afford the target compound. The amount obtained was0.189 g, and the yield was 21.4%.

The compound was identified to be the target compound based on theresults of the ¹H-NMR and FD-MS measurements.

¹H-NMR (270 MHz, CDCl₃, with reference to TMS): δ7.98 (s, 1H), 7.90 (s,1H), 7.66 (s, 1H), 7.42 (s, 1H), 6.22 (d, 1H), 5.26 (d, 1H), 3.74-3.67(m, 1H), 3.00-2.91 (m, 1H), 2.62-2.54 (m, 1H), 2.31 (s, 3H), 1.80-1.68(m, 9H), 1.55 (s, 3H), 1.42 (s, 3H), 1.40 (s, 3H), 1.39 (s, 3H), 1.28(s, 3H), 1.27 (s, 3H), 1.25 (s, 3H), 1.09 (s, 9H), 1.04 (d, 3H), 1.01(d, 3H).

FD-MS: m/Z=762.3 (Mt).

[Synthetic Example 2] Synthesis of(1-octamethylfluoren-12′-yl-3,5-di-tert-butyl-1-methyl-1,2,3,4-tetrahydropentalene)zirconium dichloride (catalyst B) (1)1,5-Di-tert-butyl-3-methyl-1,2-dihydropentalene: In a nitrogenatmosphere, a 100 ml three-necked flask was loaded with 50 ml ofcyclopentyl methyl ether and 2.5 g of tert-butylcyclopentadiene. In anice water bath, 13.2 ml of a 1.57 M hexane solution of n-butyllithiumwas added dropwise to the solution over a period of 40 minutes. Themixture was stirred at room temperature for 2 hours. In an ice waterbath, 2.02 g of pivalaldehyde was added dropwise over a period of 3minutes, and the mixture was stirred at room temperature for 3 hours.8.3m1 of pyrrolidine and 6.0 ml of acetone were added, and the mixturewas stirred at 80° C. for 16 hours. The reaction solution was pouredinto 100 ml of 1.1 N hydrochloric acid.

The organic layer was separated. The aqueous layer was extracted with100 ml of hexane. The obtained extract was combined with the previouslyseparated organic layer, and the combined organic layer was washed witha saturated aqueous sodium hydrogen carbonate solution, water and abrine. The liquid was dried with magnesium sulfate, and the solvent wasevaporated. The resultant solid was added to a mixed solvent includingethanol and methanol, and the mixture was stirred. The solidprecipitated was filtered and was dried under reduced pressure to affordthe title compound. The amount obtained was 2.09 g, and the yield was44%.

The compound was identified to be the target compound based on theresults of the ¹H-NMR measurement.

¹H-NMR (270 MHz, CDCl₃, with reference to TMS): δ5.99 (s, 1H), 5.85 (s,1H), 2.95-2.66 (m, 3H), 2.13 (s, 3H), 1.22 (s, 9H), 0.91 (s, 9H).

(2)1-Octamethylfluoren-12′-yl-3,5-di-tert-butyl-1-methyl-1,2,3,4-tetrahydropentalene:In a nitrogen atmosphere, a 100 ml three-necked flask was loaded with2.27 g of octamethylfluorene, 50 ml of cyclohexane and 1.4 ml ofcyclopentyl methyl ether. In an ice water bath, 3.90 ml of a 1.57 Mhexane solution of n-butyllithium was added dropwise over a period of 10minutes. The mixture was stirred at 50° C. for 2 hours. 1.50 g of 1,5-di-tert-butyl-3-methyl-1, 2-dihydropentalene was added, and themixture was stirred at 80° C. for 17 hours. Thereafter, the reactionsolution was added to 50 ml of 0.2 N hydrochloric acid. The organiclayer was separated. The aqueous layer was extracted with 200 ml ofhexane. The obtained extract was combined with the previously separatedorganic layer, and the combined organic layer was washed one time with asaturated aqueous sodium hydrogen carbonate solution, two times withwater, and one time with a brine. The liquid was dried with magnesiumsulfate, and the solvent was evaporated. The resultant solid waspurified by column chromatography and was washed with hexane to affordthe title compound as a light yellow powder. The amount obtained was1.91 g, and the yield was 53%.

The compound was identified to be the target compound based on theresults of the FD-MS measurement. FD-MS: m/Z=616.5 (M⁺).

¹H-NMR showed that the compound was a mixture of isomers.

(3) Catalyst (B): In a nitrogen atmosphere, a 30 ml Schlenk flask wasloaded with 1.00 g of1-octamethylfluoren-12′-yl-3,5-di-tert-butyl-1-methyl-1,2,3,4-tetrahydropentalene,0.386 g of a-methylstyrene, 16 g of cyclohexane, and 1.90 ml ofcyclopentyl methyl ether. In an oil bath at 26° C., 2.10 ml of a 1.57 Mhexane solution of n-butyllithium was added dropwise over a period of 10minutes. The mixture was stirred at 70° C. for 5 hours and was cooled inan ice/acetone bath. The liquid was degassed by evacuating the systemfor 5 minutes, and the pressure was returned to normal pressure withnitrogen. After the addition of 0.3978 g of zirconium tetrachloride, theacetone bath was removed and reaction was performed at room temperaturefor 16 hours. The solvent was evaporated, and soluble components wereextracted with hexane. The insolubles were removed by filtration, andthe insolubles were washed with hexane. The solution obtained wasconcentrated and was recrystallized in hexane. The solid was filteredand was dried under reduced pressure to afford the target compound. Theamount obtained was 0.423 g, and the yield was 34%.

The compound was identified to be the target compound based on theresults of the ¹H-NMR and FD-MS measurements.

¹H-NMR (270 MHz, CDCl₃, with reference to TMS): δ7.97 (1H, s), 7.90 (1H,s), 7.67 (1H, s), 7.43 (1H, s), 6.22 (1H, d), 5.27 (1H, d), 3.58 (1H,dd), 3.08 (1H, dd), 2.63 (1H, dd), 2.31 (3H, s), 1.784-1.661 (11H, m),1.552 (3H, s), 1.445-1.352 (3H, m), 1.30-1.28 (12H, m), 1.24 (3H, s),1.09 (9H, s), 0.98 (9H, s).

FD-MS: m/Z=776.3 (M⁺).

[Synthetic Example 3] Synthesis of(8-octamethylfluoren-12′-yl-(2-tert-butyl-8-methyl-3,3b,4,5,6,7,7a,8-octahydrocyclopenta[a]indene))zirconiumdichloride(catalyst C)

(1)2-Tert-butyl-8-methyl-3,3b,4,5,6,7,7a,8-octahydrocyclopenta[a]indene: Ina nitrogen atmosphere, a 100 ml three-necked flask was loaded with 50 mlof THF and 2.5 g of tert-butylcyclopentadiene. In an ice/acetone bath,13.0 ml of a 1.65 M hexane solution of n-butyllithium was added dropwiseto the solution over a period of 40 minutes. The mixture was stirred atroom temperature for 17 hours. In an ice water bath, 2.19 g of magnesiumchloride was added, and the mixture was stirred at room temperature for6.5 hours. 0.432 g of copper iodide was added. In an ice/acetone bath,7.08 g (38.3 wt %) of a hexane solution of 1-acetylcyclohexene was addeddropwise over a period of 10 minutes, and the mixture was stirred atroom temperature for 19 hours. 1.3 ml of acetic acid and 5.2 ml ofpyrrolidine were added, and the mixture was stirred at room temperaturefor 17 hours. The reaction solution was poured into 120 ml of 0.5 Nhydrochloric acid. The organic layer was separated. The aqueous layerwas extracted with 200 ml of hexane. The obtained extract was combinedwith the previously separated organic layer, and the combined organiclayer was washed with water, a saturated aqueous sodium hydrogencarbonate solution and a brine. The liquid was dried with magnesiumsulfate, and the solvent was evaporated. The obtained product wasrecrystallized in methanol to afford the title compound. The amountobtained was 0.445 g, and the yield was 9.5%.

The compound was identified to be the target compound based on theresults of the ¹H-NMR and GC-MS measurements.

¹H-NMR (Toluene-d8): δ6.01 (1H, s), 5.98 (1H, s), 2.88-2.73 (2H, m),1.84 (3H, s), 1.80-1.03 (17H, m).

GC-MS: m/Z=228 (M⁺).

(2) 8-Octamethylfluoren-12′-yl-(2-tert-butyl-8-methyl-3, 3b,4,5,6,7,7a,8-octahydrocyclopenta[a]indene): In a nitrogen atmosphere, a30 ml Schlenk flask was loaded with 0.655 g of octamethylfluorene and 20ml of tert-butyl methyl ether. In an ice water bath, 1.10 ml of a 1.65 Mhexane solution of n-butyllithium was added dropwise over a period of 15minutes.

The mixture was stirred for 22 hours while gradually returning thetemperature to room temperature. There was added 0.453 g of2-tert-butyl-8-methyl-3, 3b, 4,5,6,7,7a, 8-octahydrocyclopenta[a]indene. The mixture was stirred at room temperature for 19 hours andat 50° C. for 6.5 hours. Thereafter, the reaction solution was added to100 ml of 0.1 N hydrochloric acid. The organic layer was separated. Theaqueous layer was extracted with 100 ml of hexane. The obtained extractwas combined with the previously separated organic layer, and thecombined organic layer was washed one time with a saturated aqueoussodium hydrogen carbonate solution, two times with water, and one timewith a brine. The liquid was dried with magnesium sulfate, and thesolvent was evaporated. The resultant solid was purified by columnchromatography and was washed with acetone to afford the title compound.The amount obtained was 0.50 g, and the yield was 48%.

The compound was identified to be the target compound based on theresults of the FD-MS measurement. FD-MS: m/Z=614.5 (M⁺).

¹H-NMR showed that the compound was a mixture of isomers.

(3) Catalyst (C): In a nitrogen atmosphere, a 30 ml Schlenk flask wasloaded with 0.503 g of8-octamethylfluoren-12′-yl-(2-tert-butyl-8-methyl-3, 3b,4,5,6,7,7a,8-octahydrocyclopenta[a]indene, 0.193 g of α-methylstyrene,13.6 g of hexane, and 0.95 ml of cyclopentyl methyl ether. In an oilbath at 25° C., 1.00 ml of a 1.65 M hexane solution of n-butyllithiumwas added dropwise over a period of 10 minutes. The mixture was stirredat 70° C. for 4 hours and was cooled in an ice/acetone bath. The liquidwas degassed by evacuating the system for 5 minutes, and the pressurewas returned to normal pressure with nitrogen. After the addition of0.193 g of zirconium tetrachloride, the acetone bath was removed andreaction was performed at room temperature for 17 hours. The solvent wasevaporated, and soluble components were extracted with hexane. Theinsolubles were removed by filtration, and the insolubles were washedwith hexane. The solution obtained was concentrated. The supernatant wasremoved by decantation, and the solid was washed with hexane and wasdried under reduced pressure to afford the target compound. The amountobtained was 0.057 g, and the yield was 9.0%.

The compound was identified to be the target compound based on theresults of the ¹H-NMR and FD-MS measurements.

¹H-NMR (270 MHz, CDCl₃, with reference to TMS): δ7.99 (1H, s), 7.86 (1H,s), 7.61 (1H, s), 7.32 (1H, s), 6.16 (1H, s), 5.33 (1H, s), 3.58-3.49(2H, m), 2.34-2.29 (1H, m), 2.20 (3H, s), 1.93-1.19 (39H, m), 1.10 (9H,s).

FD-MS: m/Z=774.3 (Mt).

[Synthetic Example 4] Synthesis of(8-octamethylfluoren-12′-yl-(2-(adamantan-1-yl)-8-methyl-3,3b,4,5,6,7,7a,8-octahydrocyclopenta[a]indene))zirconiumdichloride(catalyst D)

(1) 1-Adamantylcyclopentadienyllithium: In a nitrogen atmosphere, a 200ml three-necked flask was loaded with a tert-butyl methyl ether solutionof ethylmagnesium bromide (1.0M, 40ml). While cooling the solution in anice bath, 2.64 g of cyclopentadiene was added dropwise over a period of20 minutes. The mixture was stirred at room temperature for 17 hours togive a solution A.

In a nitrogen atmosphere, a 500 ml three-necked flask was loaded with200 ml of diisopropyl ether and 0.36 g of copper (II)trifluoromethanesulfonate. In a water bath, the solution

A prepared above was added dropwise to the solution over a period of 20minutes. A solution of 4.30 g of 1-bromoadamantane in 40 mL ofdiisopropyl ether was added dropwise, and the mixture was stirred at 70°C. for 10 hours. The reaction liquid was cooled to room temperature. Ina water bath, 200 ml of a saturated aqueous ammonium chloride solutionwas added. The organic layer was separated. The aqueous layer wasextracted with 200 ml of hexane. The obtained extract was combined withthe previously separated organic layer, and the combined organic layerwas washed with water. The liquid was dried with magnesium sulfate, andthe solvent was evaporated. The residue was purified by silica gelcolumn chromatography to afford 4.2 g of a crude product.

In a nitrogen atmosphere, a 100 ml Schlenk flask was loaded with 4.2 gof the crude product and 20 mL of hexane. In an ice bath, 13.8 mL of a1.6 M hexane solution of n-butyllithium was added dropwise to thesolution over a period of 20 minutes. The mixture was stirred at roomtemperature for 17 hours. The precipitate was filtered out from thereaction liquid and was washed with hexane to afford the title compound.The amount obtained was 2.70 g, and the yield was 66%.

The compound was identified to be the target compound based on theresults of the ¹H-NMR measurement.

¹H-NMR (THF-d⁸): δ5.57-5.55 (2H, m), 5.52-5.50 (2H, m), 1.96 (3H, s),1.87 (6H, s), 1.74 (6H, s).

(2) 2-(Adamantan-1-yl) -8-methyl-3, 3b, 4, 5, 6, 7, 7a,8-octahydrocyclopenta[a]indene: In a nitrogen atmosphere, a 100 mlthree-necked flask was loaded with 40 ml of THF and 1.57 g of magnesiumchloride. To the solution, a solution of 3.09 g of1-adamantylcyclopentadienyllithium in 10 ml of THF was added dropwiseover a period of 5 minutes. The mixture was stirred at room temperaturefor 2 hours and at 50° C. for 3 hours. In an ice/acetone bath, asolution of 1.96 g (15.75 mmol) of 1-acetylcyclohexene in 10 ml of THFwas added dropwise over a period of 10 minutes. The mixture was stirredat room temperature for 19 hours. In an ice/acetone bath, 1.0 ml ofacetic acid and 3.1 ml of pyrrolidine were added, and the mixture wasstirred at room temperature for 17 hours. In an ice/acetone bath, 30 mlof a saturated aqueous ammonium chloride solution was added. After theaddition of 100 ml of hexane, the organic layer was separated. Theaqueous layer was extracted with 200 ml of hexane. The obtained extractwas combined with the previously separated organic layer, and thecombined organic layer was washed with water two times. The liquid wasdried with magnesium sulfate, and the solvent was evaporated. Theobtained product was recrystallized in methanol to afford the titlecompound. The amount obtained was 2.134 g, and the yield was 47%.

The compound was identified to be the target compound based on theresults of the ¹H-NMR and GC-MS measurements.

¹H-NMR (Toluene-d⁸): δ6.06 (1H, s), 5.98 (1H, s), 2.88-2.78 (2H, m),1.98-1.13 (26H, m).

GC-MS: m/Z=306 (M⁺). (3) 8-Octamethylfluoren-12′-yl-(2-(adamantan-1-yl)-8-methyl-3,3b, 4,5,6,7,7a, 8-octahydrocyclopenta [a] indene): In anitrogen atmosphere, a 30 ml Schlenk flask was loaded with 1.546 g ofoctamethylfluorene and 40 ml of tert-butyl methyl ether. In anice/acetone bath, 2.62 ml of a 1.6 M hexane solution of n-butyllithiumwas added dropwise over a period of 15 minutes. While graduallyreturning the temperature to room temperature, the mixture was stirredfor 22 hours. There was added 1.349 g of 2-(adamantan-1-yl) -8-methyl-3,3b, 4, 5, 6, 7, 7a, 8-octahydrocyclopenta [a]indene. The mixture wasstirred at room temperature for 19 hours and at 50° C. for 8 hours. Thereaction solution was added to 100 ml of a saturated aqueous ammoniumchloride solution. The organic layer was separated. The aqueous layerwas extracted with 100 ml of hexane. The obtained extract was combinedwith the previously separated organic layer, and the combined organiclayer was washed with water two times. The liquid was dried withmagnesium sulfate, and the solvent was evaporated. The resultant solidwas washed with acetone to afford the title compound. The amountobtained was 1.51 g, and the yield was 54%.

The compound was identified to be the target compound based on theresults of the FD-MS measurement. FD-MS: m/Z=693 (Mt).

¹H-NMR showed that the compound was a mixture of isomers.

(4) Catalyst (D): In a nitrogen atmosphere, a 100 ml Schlenk flask wasloaded with 1.039 g of 8-octamethylfluoren-12′-yl-(2-(adamantan-1-yl)-8-methyl-3,3b,4,5,6,7,7a,8-octahydrocyclopenta[a]indene), 0.47 ml ofa-methylstyrene, 30 ml of hexane and 2.62 ml of cyclopentyl methylether. In an oil bath at 25° C., 2.18 ml of a 1.6M hexane solution ofn-butyllithium was added dropwise over a period of 10 minutes. Themixture was stirred at 50° C. for 4 hours. The precipitate was filteredand was washed with hexane to give a pink powder. A 100 ml Schlenk flaskwas loaded with the pink powder and 30 ml of diethyl ether. After themixture was cooled in a dry ice/acetone bath, a suspension of 0.385 g(1.65 mmol) of zirconium tetrachloride in 30 ml of diethyl ether wasadded.

Thereafter, the mixture was stirred for 16 hours while graduallyincreasing the temperature to room temperature.

The solvent was removed under reduced pressure, and soluble componentswere extracted from the residue using approximately 70 ml ofdichloromethane. The solution obtained was concentrated, combined with50 ml of hexane, and filtered to remove insolubles. The solution wasconcentrated to approximately 10 ml, and the concentrate was allowed tostand overnight at −30° C. The precipitated powder was collected byfiltration and was washed with hexane to give 0.384 g of an orangepowder. The orange powder was dissolved by the addition of 5 ml ofdiethyl ether, and the solution was allowed to stand overnight at −30°C. The precipitated powder was collected by filtration and was washedwith hexane to afford the target compound. The amount obtained was 0.220g, and the yield was 17%.

The compound was identified to be the target compound based on theresults of the ¹H-NMR measurement.

¹H-NMR (270 MHz, CDCl₃, with reference to TMS): δ7.98 (1H, s), 7.86 (1H,s), 7.60 (1H, s), 7.37 (1H, s), 6.19 (1H, J=1.6Hz, d), 5.33 (1H, J=1.6Hz, d), 3.58-3.44 (2H, m), 2.35-2.28 (1H, m), 2.18 (3H, s), 1.94-1.18(54H, m).

[Synthetic Example 5] Synthesis of(1-octamethylfluoren-12′-yl-5-adamantyl-3-isopropyl-1-methyl-1,2,3,4-tetrahydropentalene)zirconium dichloride (catalyst E)

(1) 5-Adamantyl-1-isopropyl-3-methyl-1,2-dihydropentalene: In a nitrogenatmosphere, a 100 ml three-necked flask was loaded with 2.5 g ofadamantylcyclopentadienyllithium synthesized in Synthetic Example 4, and60 ml of cyclopentyl methyl ether. The flask was then placed into an icewater bath. There was added 1.33 ml of isobutylaldehyde, and the mixturewas stirred at room temperature for 17 hours. Further, 0.66 ml ofisobutylaldehyde was added, and the mixture was stirred at roomtemperature for 7 hours. Furthermore, 0.66 ml of isobutylaldehyde wasadded, and the mixture was stirred at 50° C. for 17 hours. The mixturewas then cooled to room temperature, and 5.2 ml of pyrrolidine and 4.0ml of acetone were added. Reaction was performed at 70° C. for 18 hours.A saturated aqueous ammonium chloride solution was added. The organiclayer was separated. The aqueous layer was extracted with diethyl ether.The obtained extract was combined with the previously separated organiclayer, and the combined organic layer was washed with a saturatedaqueous sodium hydrogen carbonate solution, water and a brine. Theliquid was dried with magnesium sulfate, and the solvent was evaporated.The residue was purified by column chromatography and was washed withethanol to afford the title compound. The amount obtained was 706 mg,and the yield was 20%.

The compound was identified to be the target compound based on theresults of the ¹H-NMR (CDCl₃) and FD-MS measurements.

¹H-NMR (270 MHz, CDCl₃): δ6.03 (s, 1H) , 5.83 (s, 1H), 3.07-2.97 (m,1H), 2.78-2.73 (m, 1H), 2.66-2.60 (m, 1H), 2.14-1.74 (m, 19H), 0.961 (s,3H), 0.936 (s, 3H).

FD-MS: m/Z=294.3 (Mt).

(2)1-Octamethylfluoren-12′-yl-5-adamantyl-3-isopropyl-1-methyl-1,2,3,4-tetrahydropentalene:In a nitrogen atmosphere, a 100 ml three-necked flask was loaded with893 mg of octamethylfluorene and 20 ml of tert-butyl methyl ether. 1.5ml of a 1.63 M hexane solution of n-butyllithium was added dropwise overa period of 5 minutes. The mixture was stirred at room temperature for 2hours and at 40° C. for 2 hours. The temperature was returned to roomtemperature. In an ice bath, a solution of 748 mg of5-adamantyl-1-isopropyl-3-methyl-1,2-dihydropentalene in 30 ml oftert-butyl methyl ether was added. The mixture was stirred at roomtemperature for 24 hours. A saturated aqueous ammonium chloride solutionwas added. The organic layer was separated and was washed with asaturated aqueous sodium hydrogen carbonate solution, water and a brine.The liquid was dried with magnesium sulfate, and the solvent wasevaporated. The resultant solid was washed with methanol to afford thetitle compound. The amount obtained was 1.027 g, and the yield was 64%.

The compound was identified to be the target compound based on theresults of the FD-MS measurement.

¹H-NMR showed that the compound was a mixture of isomers.

FD-MS: m/Z=680.6 (Mt).

(3) Catalyst (E): In a nitrogen atmosphere, a 100 ml Schlenk flask wasloaded with 1000 mg of1-octamethylfluoren-12′-yl-5-adamantyl-3-isopropyl-1-methyl-1,2,3,4-tetrahydropentalene,30 ml of hexane, 2.57 ml of cyclopentyl methyl ether and 0.46 ml ofa-methylstyrene. 2.16 ml of a 1.63 M hexane solution of n-butyllithiumwas added dropwise over a period of 10minutes. The mixture was stirredat 70° C. for 4 hours. The solvent was evaporated, and 20 ml of hexanewas added to the solid. The mixture was filtered to collect the solid,which was then dried under reduced pressure. The resultant solidweighing 708 mg was added to a 100 ml Schlenk flask, and 40 ml ofdiethyl ether was added. In a dry ice/methanol bath, 255 mg of zirconiumtetrachloride was added, and the mixture was stirred for 30 minutes. Thedry ice/methanol bath was removed, and the mixture was stirred for 18hours while returning the temperature to room temperature. The solventwas evaporated, and soluble components were extracted withdichloromethane and hexane. The solution obtained was concentrated andwas dissolved in 2 ml of hexane. Recrystallization was performed at −20°C. The resultant red solid precipitate was recovered by filtration,washed with hexane, and dried under reduced pressure to afford the titlecompound. The amount obtained was 207.6 mg, and the yield was 17%.

The compound was identified to be the target compound based on theresults of the ¹H-NMR (CDCl₃) and FD-MS measurements.

¹H-NMR (270 MHz, CDCl₃): δ7.97 (s, 1H), 7.89 (s, 1H), 7.65 (s, 1H), 7.42(s, 1H), 6.24 (d, 1H), 5.25 (d, 1H), 3.74-3.67 (m, 1H), 3.00-2.91 (m,1H), 2.62-2.53 (m, 1H), 2.30 (s, 3H), 1.88-1.24 (m, 48H), 1.04 (d, 3H),1.01 (d, 3H).

FD-MS: m/Z=840.3 (M⁺).

[Comparative Synthetic Example 1] Synthesis of[3-(octamethylfluoren-12′-yl)(1,1,3-trimethyl-5-tert-butyl-1,2,3,3a-tetrahydropentalene) zirconiumdichloride (catalyst a)

(1) 5-Tert-butyl-1,1,3-trimethyl-1,2-dihydropentalene: In a nitrogenatmosphere, a 200 ml three-necked flask was loaded with 4.83 g oftert-butylcyclopentadiene, 9.0 ml of 4-methylpent-3-en-2-one, 40 ml ofmethanol and 16.5 ml of pyrrolidine. The mixture was stirred for 43hours under reflux. The reaction solution was poured into 250 ml of 1 Nhydrochloric acid. The organic layer was separated. The aqueous layerwas extracted with 200 ml of hexane. The obtained extract was combinedwith the previously separated organic layer, and the combined organiclayer was washed with water and a brine. The liquid was dried withmagnesium sulfate, and the solvent was evaporated. The residue waspurified by column chromatography to afford the title compound. Thepurity was determined to be 86.8% by gas chromatography. The amountobtained was 5.46 g, and the yield was 59.4%.

¹H-NMR (270 MHz, CDCl₃, with reference to TMS): δ5.87 (s, 1H), 5.79 (s,1H), 2.94 (d, 1H), 2.10 (t, 3H), 1.27 (s, 1H), 1.21 (s, 9H).

GC-MS: m/Z=202 (Mt).

(2) 3-(Octamethylfluoren-12′-yl)(1,1,3-trimethyl-5-tert-butyl-1,2,3,3a-tetrahydropentalene): In anitrogen atmosphere, a 100 ml three-necked flask was loaded with 1.58 gof octamethylfluorene and 30 ml of diethyl ether. In an ice/acetonebath, 2.7 ml of a 1.56 M hexane solution of n-butyllithium was addeddropwise over a period of 15 minutes. The mixture was stirred for 25hours while gradually increasing the temperature to room temperature. 10ml of a diethyl ether solution of 0.95 g of5-tert-butyl-1,1,3-trimethyl-1,2-dihydropentalene was added over aperiod of 5minutes. The mixture was stirred for 56 hours under reflux.The reaction solution was poured into 100 ml of 1 N hydrochloric acid.The organic layer was separated. The aqueous layer was extracted with 75ml of hexane two times. The obtained extract was combined with thepreviously separated organic layer, and the combined organic layer waswashed one time with a saturated aqueous sodium hydrogen carbonatesolution, two times with water, and one time with a brine. The liquidwas dried with magnesium sulfate, and the solvent was evaporated. Theresultant solid was purified by column chromatography and was washedwith pentane and ethanol to afford the title compound. The amountobtained was 2.02 g, and the yield was 84%.

The compound was identified to be the target compound based on theresults of the ¹H-NMR and FD-MS measurements.

¹H-NMR (270 MHz, CDCl₃, with reference to TMS): δ7.58 (s, 1H), 7.55+7.54(s, 1H), 7.50+7.49 (s, 1H), 6.89+6.46 (s, 1H), 6.32+5.93 (s, 1H),3.87+3.83 (s, 1H), 3.11 (q, 1H), 2.68 (d, 1H), 1.71 (s, 3H), 1.67-1.61(m, 8H), 1.38-1.28 (m, 27H), 1.18-0.95 (m, 11H), 0.27+0.21 (s, 3H).

FD-MS: m/Z=589 (Mt).

(3) Catalyst (a): In a nitrogen atmosphere, a 30 ml Schlenk flask wasloaded with 0.884 g of 3-(octamethylfluoren-12′-yl)(1,1,3-trimethyl-5-tert-butyl-1,2,3,3a-tetrahydropentalene) and 20 ml ofhexane. In an ice/acetone bath, 2.05 ml of a 1.56 M hexane solution ofn-butyllithium was added, and the mixture was stirred for 15 minutes.0.351 g (3.12 mmol) of tert-butoxypotassium was added. The mixture wasstirred for 5 hours while gradually returning the temperature to roomtemperature. Thereafter, the mixture was filtered to give a red purplepowder. The red purple powder was washed with approximately 10 ml ofhexane. The red purple powder and 30 ml of diethyl ether were added to a30 ml Schlenk flask. After cooling in an ice/acetone bath, 0.452 g (1.94mmol) of zirconium tetrachloride was added. The mixture was stirred for39 hours while gradually returning the temperature to room temperature.The solvent was evaporated, and soluble components were extracted withdichloromethane. The solvent was evaporated. Hexane was added to thesolid obtained, and soluble components were extracted. The hexanesolution was concentrated, and a solid was precipitated, removed bydecantation, and dried under reduced pressure to afford the targetcompound. The amount obtained was 0.248 g, and the yield was 22.2%.

The compound was identified to be the target compound based on theresults of the ¹H-NMR and FD-MS measurements.

¹H-NMR (270 MHz, CDCl₃, with reference to TMS): δ7.99 (s, 1H), 7.98 (s,1H), 7.78 (s, 1H), 7.54 (s, 1H), 6.01 (d, 1H), 5.25 (d, 1H), 3.94 (d,1H), 2.62 (d, 1H), 2.31 (s, 3H), 1.79-1.61 (m, 8H), 1.57 (s, 3H), 1.43(s, 3H), 1.41 (s, 3H), 1.39 (s, 9H), 1.35 (s, 3H), 1.32 (s, 3H), 1.28(s, 3H), 1.24 (s, 3H), 1.09 (s, 9H).

FD-MS: m/Z=748 (Mt).

[Comparative Synthetic Example 2] Metallocene compound synthesized inaccordance with Synthetic Example 1 of WO 2006/025540(diphenylmethylene(3-tert-butyl-5-ethylcyclopentadienyl)(2,7-di-tert-butylfluorenyl)zirconium dichloride; catalyst b)

[Comparative Synthetic Example 3] Metallocene compound synthesized inaccordance with Example 1 of WO 2001/027124(dimethylmethylene(3-tert-butyl-5-methylcyclopentadienyl)fluorenylzirconiumdichloride; catalyst c) [Comparative Synthetic Example 4] Metallocenecompound synthesized in accordance with Example 3c of WO2004/087775(diphenylmethylene(3-tert-butyl-5-methylcyclopentadienyl)(2,7-di-tert-butylfluorenyl)zirconium dichloride; catalyst d)

Example 1A

A 500 ml-volume gas-flow glass polymerization reactor that had beenthoroughly purged with nitrogen was loaded with 250 ml of hexane. At 25°C., 1-butene was supplied at 90 L/h and the system was thoroughlysaturated with the gas. Next, 0.25 mmol of triisobutylaluminum wasadded. Further, there was added a hexane solution of a mixture including10 μmol of a transition metal compound (the catalyst B) and 5.0 mmol (interms of Al atoms) of methylaluminoxane (MMAO-3A) manufactured by TOSOFINECHEM CORPORATION. Polymerization was performed for 45 minutes whilemaintaining the system at 25° C. The polymerization was terminated byadding a small amount of isobutyl alcohol. The polymerization suspensionwas added to 1 L of a methanol-acetone mixed solvent (1:1 by volume)containing a small amount of hydrochloric acid, and the mixture wassufficiently stirred and filtered. The polymer was washed with a largeamount of methanol and was dried at 80° C. for 10 hours. The results aredescribed in Table 1.

Examples 2A to 4A and Comparative Examples 1A and 2A

Polymerization was performed by the same process as in Example 1A,except that the type and the amount of the transition metal compound andthe amount of methylaluminoxane in the hexane solution, and thepolymerization conditions in Example 1A were changed as described inTable 1. The results are described in Table 1 and Table 2.

TABLE 1 Polymer- ization Polymer- Catalytic Hexane solution 1- Hydro-temper- ization Yield activity Transition metal Methylaluminoxane Butenegen ature time amount kg/mmol- Tm Mw Mw/ compound (in terms of Al atoms)L/h L/h ° C. min g Zr/h ° C. ×10⁴ Mn Ex. 1A Cata- 10 μmol MMAO- 5.0 mmol90 0.00 25 45 9.27 1.0 128.2 74.5 1.92 lyst B 3A Ex. 2A Cata- 0.60 μmolMMAO- 0.30 mmol 90 0.25 25 45 1.80 4.0 129.4 243 2.75 lyst B 3A Ex. 3ACata- 10 μmol MMAO- 5.0 mmol 90 0.00 25 7.0 6.33 5.0 126.7 35.4 2.04lyst C 3A Ex. 4A Cata- 0.60 μmol MMAO- 0.30 mmol 90 0.25 25 25 2.59 1.0× 10¹  128.5 163 2.53 lyst C 3A Comp. Cata- 10 μmol MMAO- 5.0 mmol 900.00 25 60 0.25 2.5 × 10⁻² 120.4 3.58 1.27 Ex. 1A lyst a 3A Comp. Cata-0.60 μmol MMAO- 0.30 mmol 90 0.25 25 60 0.43 7.1 × 10⁻¹ 123.5 59.5 2.24Ex. 2A lyst a 3A *Hydrogen was supplied together with 1-butene.

TABLE 2 1-Butene homopolymerization Tm TmII Tc mmmm Mw Catalyst ° C. °C. ° C. % Regioerrors ×10⁴ Mw/Mn Ex. 2A Catalyst B 129.4 122.0 75.5 99.3Below detection limit 243 2.75 Ex. 4A Catalyst C 128.5 119.7 72.6 99.3Below detection limit 163 2.53 Comp. Ex. 2A Catalyst a 123.5 111.3 67.297.5 Below detection limit 59.5 2.24

Example 5A

A stirrer was placed into a 30 mL branched flask that had been purgedwith nitrogen. The flask was then loaded with 3.9 mg of a transitionmetal compound (the catalyst D), 5 mL of heptane and 0.35 mL ofmethylaluminoxane (TMAO-341) manufactured by TOSO FINECHEM CORPORATION(Al/Zr=310 by mol). The mixture was stirred for at least 30 minutes togive a catalyst solution.

A 1,500 mL-volume SUS autoclave that had been purged with nitrogen wasloaded with 500 mL of heptane and 1.5 mL of a 0.5 M heptane solution oftriisobutylaluminum and thereafter with 100 g of 1-butene. The autoclavewas heated to 70° C., and nitrogen was supplied to control the autoclaveinside pressure to 0.50 MPaG.

The whole amount of the catalyst solution was added to the autoclave,and polymerization was performed at 70° C. for 20 minutes. Thepolymerization was terminated by adding methanol to the autoclave. Theresultant polymer solution was added to 2 L of a methanol-acetone mixedsolvent (1:1 by volume) and thereby the polymer was precipitated. Thepolymer was dried under reduced pressure at 80° C. for 10 hours. Theresults are described in Table 3-1.

Example 6A

Polymerization was performed by the same process as in Example 5A,except that the polymerization temperature in Example 5A was changed to40° C. The results are described in Table 3-1.

Example 7A

Polymerization was performed by the same process as in

Example 5A, except that the amount of 1-butene and the polymerizationtemperature in Example 5A were changed to 180 g and 50° C. The resultsare described in Table 3-1 and Table 3-2. The obtained polymer will bewritten as Xl.

Example 8A

Polymerization was performed by the same process as in Example 7A,except that the polymerization temperature in Example 7A was changed to60° C. The results are described in Table 3-1.

Example 9A

Polymerization was performed by the same process as in Example 7A,except that the amounts of the transition metal compound and themethylaluminoxane, and the polymerization temperature in Example 7A werechanged as described in Table 3-1, that the addition of 1-butene wasfollowed by the addition of 0.06 NL of hydrogen, and that thepolymerization temperature was changed to 60° C. The results aredescribed in Table 3-1.

Example 10A

Polymerization was performed by the same process as in Example 7A,except that the amounts of the transition metal compound and themethylaluminoxane, and the polymerization temperature in Example 7A werechanged as described in Table 3-1, that the addition of 1-butene wasfollowed by the addition of 0.13 NL of hydrogen, and that thepolymerization temperature was changed to 60° C. The results aredescribed in Table 3-1 and Table 3-2. The obtained polymer will bewritten as X2. The results of cross fractionation chromatography (CFC)with respect to the polymer X2 are described in Table 3-3.

Comparative Example 3A

Polymerization was performed by the same process as in Example 7A,except that the type of the transition metal compound in Example 7A waschanged as described in Table 3-1, that the addition of 1-butene wasfollowed by the addition of 0.012 NL of hydrogen, and that thepolymerization temperature was changed to 40° C. The results aredescribed in Table 3-1 and Table 3-2. The obtained polymer will bewritten as X3.

Comparative Example 4A

Polymerization was performed by the same process as in

Example 7A, except that the type of the transition metal compound, andthe amounts of the transition metal compound and the methylaluminoxanein Example 7A were changed as described in Table 3-1, and that thepolymerization temperature was changed to 60° C. The results aredescribed in Table 3-1. The obtained polymer will be written as X4. Theresults of cross fractionation chromatography (CFC) with respect to thepolymer X4 are described in Table 3-3.

TABLE 3-1 1-Butene pressure homopolymerization Polymer- ization Polymer-Catalytic Amount of Amount of Amount of Amount of temper- ization Yieldactivity catalyst co-catalyst solvent butene ature time amount (kg/mmol-[η] Tm Tc Catalyst μmol mmol L g ° C. min g Zr · h) dl/g ° C. ° C.Polymer Ex. 5A Catalyst D 4.3 1.36 0.5 100 70 20 14.0 9.8 1.46 121.758.4 — Ex. 6A Catalyst D 4.3 1.36 0.5 100 40 20 9.6 6.7 3.29 128.1 71.5— Ex. 7A Catalyst D 4.3 1.36 0.5 180 50 20 38.0 26.6 3.68 128.7 71.4 X1Ex. 8A Catalyst D 4.3 1.36 0.5 180 60 20 36.6 25.5 2.81 127.8 71.4 — Ex.9A Catalyst D 0.23 0.07 0.5 180 60 20 5.9 77.8 2.38 128.7 67.6 — Ex. 10ACatalyst D 0.46 0.14 0.5 180 60 20 21.4 140.1 1.59 128.1 68.9 X2 Comp.Catalyst c 4.3 1.36 0.5 180 40 20 26.0 18.1 3.29 128.8 66.8 X3 Ex. 3AComp. Catalyst c 12.9 4.08 0.5 180 60 20 17.6 4.1 1.33 120.7 67.0 X4 Ex.4A

TABLE 3-2 1-Butene pressure homopolymerization Tensile yield Tensilestress mmmm stress at break Tensile modulus Polymer Mw/Mn % RegioerrorsMPa MPa MPa X1 2.5 98.3 Below detection limit 18.1 45.5 465.3 X2 2.198.5 Below detection limit 20.4 41.7 530.0 X3 2.3 94.0 Below detectionlimit 16.5 46.3 394.4 X4 2.2 94.5 Below detection limit 18.8 40.5 444.2

The properties in Table 3-2 were evaluated in the following manner.

<Tensile Yield Stress, Tensile Stress at Break and Tensile Modulus ofButene Homopolymers>

In accordance with JIS K 7113, a JIS K 7113 No. 2 test piece 1/2 thathad been punched out from a 2 mm thick compression molded sheet obtainedas described below was used as an evaluation sample and was tested at23° C. and a tension rate of 30 mm/min (measurement apparatus: model202X-5 manufactured by INTESCO Co., Ltd.).

<Compression Molding Conditions>

Compression molded sheets were produced under the following conditionsand were stored at room temperature for 10 days before the testing.

Compression molding machine: manufactured by Kansai Roll Co., Ltd.(model: PEWE-70/50 35)

Heating time: 5 min

Heating temperature: 190° C.

Pressure during heating: 10 MPa

Cooling rate: at least 40° C./min (The sheet was cooled to roomtemperature by being compression molded on a separate compressionmolding machine set at 20° C. and 10 MPa for 4 minutes.)

TABLE 3-3 Results of cross fractionation chromatography (CFC) Polymer X2X4 Elution start temperature [TS] (° C.) 46 46 Elution end temperature[TE] (° C.) 60 60 Accumulated elution amount at [TX] (wt %) 46.9 37.4

The CFC elution curve of the 1-butene polymer X2 is illustrated in FIG.1A, and the CFC elution curve of the 1-butene polymer X4 is illustratedin FIG. 1B.

<Evaluations>

The polymer X2 was such that the mmmm was not less than 98.0% and theaccumulated elution amount at a temperature [T_(X)] defined as([T_(S)]+[T_(E)])/2 was not less than 40 wt %. As shown in Table 3-2,the polymer X2 exhibited a high tensile modulus while having a tensileyield stress similar to that of conventional polymers (for example,polymer X4). This result shows that the novel 1-butene polymers of theinvention are excellent in the balance between rigidity and yieldstress.

Example 1B

A stirrer was placed into a 30 mL branched flask that had been purgedwith nitrogen. The flask was then loaded with 4.6 mg of a transitionmetal compound (the catalyst C), 22.0 mL of toluene and 0.58 mL ofmethylaluminoxane (TMAO-341) manufactured by TOSO FINECHEM CORPORATION(Al/Zr=300 by mol). The mixture was stirred for at least 30 minutes togive a catalyst solution containing the catalyst C with a concentrationof 0.25 mmol/L.

In a nitrogen atmosphere, a reactor of a parallel polymerization reactormanufactured by Biotage Japan Ltd. was loaded with 0.4 mL of a 0.05 M4-methyl-1-pentene solution of triisobutylaluminum, and 2.7 mL of4-methyl-1-pentene. The mixture was heated to 70° C.

0.2 mL of the catalyst solution was fed to the reactor, and subsequently0.7 mL of toluene was added, thereby initiating polymerization. Thepolymerization was performed for 20 minutes and was terminated by theaddition of isobutyl alcohol. The resultant polymer solution was addedto methanol to precipitate the polymer. The polymer was dried at 80° C.under reduced pressure for 12 hours. The results are described in Table4.

Examples 2B to 4B and Comparative Example 1B

Polymerization was performed by the same process as in Example 1B,except that the type of the transition metal compound and the catalystconcentration in the catalyst solution in Example 1B were changed asdescribed in Table 4. The results are described in Table 4.

TABLE 4 4-Methyl-1-pentene homopolymerization Amount of Yield CatalyticCatalyst catalyst amount activity Mw Mn Tm Tc Catalyst concentrationμmol mg kg/mmol-Zr/h ×10⁴ ×10⁴ ° C. ° C. Ex. 1B Catalyst C 0.25 mmol/L0.050 113 6.8 70.8 32.2 241.1 214.4 Ex. 2B Catalyst A 0.50 mmol/L 0.10578 17 131 53.2 241.7 212.3 Ex. 3B Catalyst D 0.25 mmol/L 0.050 144 8.778.0 33.2 242.9 217.1 Ex. 4B Catalyst E 0.50 mmol/L 0.10 279 8.4 241 102243.6 216.0 Comp. Catalyst a 0.50 mmol/L 0.10 106 3.2 28.5 14.3 234.8211.6 Ex. 1B

Example 1C

A stirrer was placed into a 30 mL branched flask that had been purgedwith nitrogen. The flask was then loaded with 3.4 mg of a transitionmetal compound (the catalyst D), 5 mL of toluene and 0.30 mL ofmethylaluminoxane (TMAO-341) manufactured by TOSO FINECHEM CORPORATION(Al/Zr=310 by mol). The mixture was stirred for at least 30 minutes togive a catalyst solution.

A 1,500 mL-volume SUS autoclave that had been purged with nitrogen wasloaded with 750 mL of 4-methyl-1-pentene, 75 mL of 1-octene and 1.5 mLof a 0.5 M toluene solution of triisobutylaluminum. The autoclave washeated to 50° C.

The whole amount of the catalyst solution was added to the autoclave,and polymerization was performed at 50° C. for 15 minutes. Thepolymerization was terminated by adding methanol to the autoclave. Theresultant polymer solution was added to 2 L of a methanol-acetone mixedsolvent (1:1 by volume) and thereby the polymer was precipitated. Thepolymer was dried under reduced pressure at 80° C. for 10 hours. Theresults are described in Table 5.

Examples 2C to 4C

Polymerization was performed by the same process as in Example 1C,except that the amount of octene and the polymerization time in Example1C were changed as described in Table 5. The results are described inTable 5.

Example 5C

A stirrer was placed into a 30 mL branched flask that had been purgedwith nitrogen. The flask was then loaded with 4.4 mL of a toluenesolution containing 0.25 mg/mL of a transition metal compound (thecatalyst D), and 0.10 mL of methylaluminoxane (TMAO-341) manufactured byTOSO FINECHEM CORPORATION (Al/Zr=310 by mol). The mixture was stirredfor at least 30 minutes to give a catalyst solution.

A 1,500 mL-volume SUS autoclave that had been purged with nitrogen wasloaded with 750 mL of 4-methyl-1-pentene, 8 mL of 1-octene and 1.5 mL ofa 0.5 M toluene solution of triisobutylaluminum. The autoclave washeated to 50° C.

After 0.25 NL of hydrogen was fed to the autoclave, the whole amount ofa solution of 0.2 mL of the catalyst solution in 4.8 mL of toluene wasadded. Polymerization was performed at 50° C. for 15 minutes and wasterminated by the addition of methanol. The resultant polymer solutionwas added to 2 L of a methanol-acetone mixed solvent (1:1 by volume) andthereby the polymer was precipitated. The polymer was dried underreduced pressure at 80° C. for 10 hours. The results are described inTable 5.

Examples 6C to 8C

Polymerization was performed by the same process as in Example 5C,except that the amounts of octene and hydrogen, and the polymerizationtime in Example 5C were changed as described in Table 5. The results aredescribed in Table 5.

Example 9C

A stirrer was placed into a 30 mL branched flask that had been purgedwith nitrogen. The flask was then loaded with 3.4 mg of a transitionmetal compound (the catalyst D), 5 mL of toluene, and 0.30 mL ofmethylaluminoxane (TMAO-341) manufactured by TOSO FINECHEM CORPORATION(Al/Zr=310 by mol). The mixture was stirred for at least 30 minutes togive a catalyst solution.

A 1,500 mL-volume SUS autoclave that had been purged with nitrogen wasloaded with 400 mL of 4-methyl-1-pentene, 350 mL of cyclohexane, 4 mL of1-octene and 1.5 mL of a 0.5 M toluene solution of triisobutylaluminum.The autoclave was heated to 65° C.

The whole amount of the catalyst solution was added to the autoclave,and polymerization was performed at 65° C. for 20 minutes. Thepolymerization was terminated by adding methanol to the autoclave. Theresultant polymer solution was added to 2 L of a methanol-acetone mixedsolvent (1:1 by volume) and thereby the polymer was precipitated. Thepolymer was dried under reduced pressure at 80° C. for 10 hours. Theresults are described in Table 5.

Example 10C

Polymerization was performed by the same process as in Example 9C,except that the transition metal compound in Example 9C was changed to3.4 mg of the catalyst E. The results are described in Table 5.

Example 11C

A stirrer was placed into a 30 mL branched flask that had been purgedwith nitrogen. The flask was then loaded with 4.6 mg of a transitionmetal compound (the catalyst E), 8.8 mL of toluene, and 0.41 mL ofmethylaluminoxane (TMAO-341) manufactured by TOSO FINECHEM CORPORATION(Al/Zr=310 by mol). The mixture was stirred for at least 30 minutes togive a catalyst solution.

A 1,500 mL-volume SUS autoclave that had been purged with nitrogen wasloaded with 400 mL of 4-methyl-1-pentene, 350 mL of cyclohexane, 4 mL of1-octene and 1.5 mL of a 0.5 M toluene solution of triisobutylaluminum.The autoclave was heated to 65° C.

After 0.06 NL of hydrogen was fed to the autoclave, the whole amount ofa solution of 0.4 mL of the catalyst solution in 4.6 mL of toluene wasadded. Polymerization was performed at 65° C. for 20 minutes and wasterminated by the addition of methanol. The resultant polymer solutionwas added to 2 L of a methanol-acetone mixed solvent (1:1 by volume) andthereby the polymer was precipitated. The polymer was dried underreduced pressure at 80° C. for 10 hours. The results are described inTable 5.

TABLE 5 4-Methyl-1-pentene/1-octene copolymerization Amount of Amount ofAmount of Polymerization Polymerization Yield Catalytic catalyst octenehydrogen temperature time amount activity [η] Tm Tc Example Catalystμmol Ml NL ° C. min g kg/mmol-Zr/h dl/g ° C. ° C. Ex. 1C Catalyst D 3.775 0.00 50 15 13.85 1.5 × 10¹ 6.63 179.7 149.7 Ex. 2C Catalyst D 3.7 380.00 50 12 11.86 1.6 × 10¹ 6.52 207.9 178.2 Ex. 3C Catalyst D 3.7 260.00 50 10 10.54 1.7 × 10¹ 6.30 217.3 188.2 Ex. 4C Catalyst D 3.7 8 0.0050 10 11.12 1.8 × 10¹ 6.73 231.6 203.4 Ex. 5C Catalyst D 0.055 8 0.25 5015 17.78 1.3 × 10³ 2.89 234.2 204.2 Ex. 6C Catalyst D 0.055 8 0.31 50 203.77 2.1 × 10² 2.40 233.8 204.5 Ex. 7C Catalyst D 0.055 26 0.25 50 1526.14 1.9 × 10³ 2.75 219.7 190.0 Ex. 8C Catalyst D 0.055 26 0.31 50 209.62 5.2 × 10² 2.31 219.3 189.5 Ex. 9C Catalyst D 3.7 4 0.00 65 20 13.651.0 × 10¹ 3.35 233.2 204.1 Ex. 10C Catalyst E 3.8 4 0.00 65 20 6.60 5.34.68 231.6 205.9 Ex. 11C Catalyst E 0.22 4 0.06 65 20 53.0 7.2 × 10³2.06 234.2 207.8

Example 1D

A stirrer was placed into a 30 mL branched flask that had been purgedwith nitrogen. The flask was then loaded with 1.1 mg of a transitionmetal compound (the catalyst C), 5 mL of toluene and 0.11 mL ofmethylaluminoxane (TMAO-341) manufactured by TOSO FINECHEM CORPORATION(Al/Zr=310 by mol). The mixture was stirred for at least 30 minutes togive a catalyst solution.

A 1,500 mL-volume SUS autoclave that had been purged with nitrogen wasloaded with 750 mL of 4-methyl-1-pentene and 1.5 mL of a 0.5 M toluenesolution of triisobutylaluminum. The autoclave was heated to 70° C., andnitrogen was supplied to control the autoclave inside pressure to 0.30MPaG. Thereafter, propylene was supplied to control the pressure to 0.50MPaG.

The whole amount of the catalyst solution was added to the autoclave,and polymerization was performed at 70° C. for 20 minutes. During thepolymerization, propylene was supplied to maintain the autoclave insidepressure at 0.50 MPaG. The polymerization was terminated by addingmethanol to the autoclave. The resultant polymer solution was added to 2L of a methanol-acetone mixed solvent (1:1 by volume) and thereby thepolymer was precipitated. The polymer was dried under reduced pressureat 80° C. for 12 hours. The results are described in Table 6.

Example 2D

A stirrer was placed into a 30 mL branched flask that had been purgedwith nitrogen. The flask was then loaded with 3.3 mg of a transitionmetal compound (the catalyst C), 5 mL of toluene and 0.30 mL ofmethylaluminoxane (TMAO-341) (Al/Zr =310 by mol). The mixture wasstirred for at least 30 minutes to give a catalyst solution.

A 1,500 mL-volume SUS autoclave that had been purged with nitrogen wasloaded with 750 mL of 4-methyl-1-pentene and 1.5 mL of a 0.5 M toluenesolution of triisobutylaluminum. The autoclave was heated to 70° C., andnitrogen was supplied to control the autoclave inside pressure to 0.40MPaG. Thereafter, propylene was supplied to control the pressure to 0.50MPaG.

The whole amount of the catalyst solution was added to the autoclave,and polymerization was performed at 70° C. for 20 minutes. During thepolymerization, propylene was supplied to maintain the autoclave insidepressure at 0.50 MPaG. The polymerization was terminated by addingmethanol to the autoclave. The rest of the procedure was the same as inExample 1D. The results are described in Table 6.

Example 3D

A stirrer was placed into a 30 mL branched flask that had been purgedwith nitrogen. The flask was then loaded with 2.2 mg of a transitionmetal compound (the catalyst C), 5 mL of toluene and 0.22 mL ofmethylaluminoxane (TMAO-341) (Al/Zr=310 by mol). The mixture was stirredfor at least 30 minutes to give a catalyst solution.

A 1,500 mL-volume SUS autoclave that had been purged with nitrogen wasloaded with 750 mL of 4-methyl-1-pentene and 1.5 mL of a 0.5 M toluenesolution of triisobutylaluminum. The autoclave was heated to 70° C., andnitrogen was supplied to control the autoclave inside pressure to 0.45MPaG. Thereafter, propylene was supplied to control the pressure to 0.50MPaG.

The whole amount of the catalyst solution was added to the autoclave,and polymerization was performed at 70° C. for 20 minutes. During thepolymerization, propylene was supplied to maintain the autoclave insidepressure at 0.50 MPaG. The polymerization was terminated by addingmethanol to the autoclave. The rest of the procedure was the same as inExample 1D. The results are described in Table 6.

Example 4D

A stirrer was placed into a 30 mL branched flask that had been purgedwith nitrogen. The flask was then loaded with 3.5 mg of a transitionmetal compound (the catalyst D), 5 mL of toluene and 0.35 mL ofmethylaluminoxane (TMAO-341) (Al/Zr=310 by mol). The mixture was stirredfor at least 30 minutes to give a catalyst solution.

A 1,500 mL-volume SUS autoclave that had been purged with nitrogen wasloaded with 750 mL of 4-methyl-1-pentene and 1.5 mL of a 0.5 M toluenesolution of triisobutylaluminum. The autoclave was heated to 70° C.After the addition of 0.13 NL of hydrogen to the autoclave, nitrogen wassupplied to control the autoclave inside pressure to 0.40 MPaG.Thereafter, propylene was supplied to control the pressure to 0.50 MPaG.

The whole amount of a solution of 0.2 mL of the catalyst solution in 4.8mL of toluene was added to the autoclave, and polymerization wasperformed at 70° C. for 10 minutes. During the polymerization, propylenewas supplied to maintain the autoclave inside pressure at 0.50 MPaG. Thepolymerization was terminated by adding methanol to the autoclave. Therest of the procedure was the same as in Example 1D. The results aredescribed in Table 6.

Example 5D

A stirrer was placed into a 30 mL branched flask that had been purgedwith nitrogen. The flask was then loaded with 2.9 mg of a transitionmetal compound (the catalyst D), 2.9 mL of toluene and 0.25 mL ofmethylaluminoxane (TMAO-341) (Al/Zr=310 by mol). The mixture was stirredfor at least 30 minutes to give a catalyst solution.

A 1,500 mL-volume SUS autoclave that had been purged with nitrogen wasloaded with 750 mL of 4-methyl-1-pentene and 1.5 mL of a 0.5 M toluenesolution of triisobutylaluminum. The autoclave was heated to 80° C.After the addition of 0.06 NL of hydrogen to the autoclave, nitrogen wassupplied to control the autoclave inside pressure to 0.40 MPaG.Thereafter, propylene was supplied to control the pressure to 0.50 MPaG.

The whole amount of a solution of 0.2 mL of the catalyst solution in 4.8mL of toluene was added to the autoclave, and polymerization wasperformed at 80° C. for 10 minutes. During the polymerization, propylenewas supplied to maintain the autoclave inside pressure at 0.50 MPaG. Thepolymerization was terminated by adding methanol to the autoclave. Therest of the procedure was the same as in Example 1D. The results aredescribed in Table 6.

Example 6D

A stirrer was placed into a 30 mL branched flask that had been purgedwith nitrogen. The flask was then loaded with 1.7 mg of a transitionmetal compound (the catalyst D), 5 mL of toluene and 0.15 mL ofmethylaluminoxane (TMAO-341) (Al/Zr=310 by mol). The mixture was stirredfor at least 30 minutes to give a catalyst solution.

A 1,500 mL-volume SUS autoclave that had been purged with nitrogen wasloaded with 750 mL of 4-methyl-1-pentene and 1.5 mL of a 0.5 M toluenesolution of triisobutylaluminum. The autoclave was heated to 70° C., andnitrogen was supplied to control the autoclave inside pressure to 0.25MPaG. Thereafter, propylene was supplied to control the pressure to 0.50MPaG.

The whole amount of the catalyst solution was added to the autoclave,and polymerization was performed at 70° C. for 20 minutes. During thepolymerization, propylene was supplied to maintain the autoclave insidepressure at 0.50 MPaG. The polymerization was terminated by addingmethanol to the autoclave. The rest of the procedure was the same as inExample 1D. The results are described in Table 6.

Example 7D

A stirrer was placed into a 30 mL branched flask that had been purgedwith nitrogen. The flask was then loaded with 3.2 mg of a transitionmetal compound (the catalyst D), 3.2 mL of toluene and 0.15 mL ofmethylaluminoxane (TMAO-341) (Al/Zr=310 by mol). The mixture was stirredfor at least 30 minutes to give a catalyst solution.

A 1,500 mL-volume SUS autoclave that had been purged with nitrogen wasloaded with 750 mL of 4-methyl-1-pentene and 1.5 mL of a 0.5 M toluenesolution of triisobutylaluminum. The autoclave was heated to 70° C., andnitrogen was supplied to control the autoclave inside pressure to 0.20MPaG. Thereafter, propylene was supplied to control the pressure to 0.50MPaG.

1.7 mL of the catalyst solution was added to the autoclave, andpolymerization was performed at 70° C. for 20 minutes. During thepolymerization, propylene was supplied to maintain the autoclave insidepressure at 0.50 MPaG. The polymerization was terminated by addingmethanol to the autoclave. The rest of the procedure was the same as inExample 1D. The results are described in Table 6.

Example 8D

Polymerization was performed by the same process as in Example 2D,except that the transition metal compound in Example 2D was changed to3.0 mg of the catalyst A. The results are described in Table 6.

Example 9D

A stirrer was placed into a 30 mL branched flask that had been purgedwith nitrogen. The flask was then loaded with 4.2 mg of a transitionmetal compound (the catalyst E), 6.2 mL of toluene and 0.37 mL ofmethylaluminoxane (TMAO-341) (Al/Zr=310 by mol). The mixture was stirredfor at least 30 minutes to give a catalyst solution.

A 1,500 mL-volume SUS autoclave that had been purged with nitrogen wasloaded with 750 mL of 4-methyl-1-pentene and 1.5 mL of a 0.5 M toluenesolution of triisobutylaluminum. The autoclave was heated to 70° C., andnitrogen was supplied to control the autoclave inside pressure to 0.20MPaG. Thereafter, propylene was supplied to control the pressure to 0.60MPaG.

5.3 mL of the catalyst solution was added to the autoclave, andpolymerization was performed at 70° C. for 20 minutes. During thepolymerization, propylene was supplied to maintain the autoclave insidepressure at 0.60 MPaG. The polymerization was terminated by addingmethanol to the autoclave. The rest of the procedure was the same as inExample 1D. The results are described in Table 6.

Example 10D

A stirrer was placed into a 30 mL branched flask that had been purgedwith nitrogen. The flask was then loaded with 2.9 mg of a transitionmetal compound (the catalyst E), 2.7 mL of toluene and 0.26 mL ofmethylaluminoxane (TMAO-341) (Al/Zr=310 by mol). The mixture was stirredfor at least 30 minutes to give a catalyst solution.

A 1,500 mL-volume SUS autoclave that had been purged with nitrogen wasloaded with 750 mL of 4-methyl-1-pentene and 1.5 mL of a 0.5 M toluenesolution of triisobutylaluminum. The autoclave was heated to 70° C.After the addition of 0.06 NL of hydrogen to the autoclave, nitrogen wassupplied to control the autoclave inside pressure to 0.20 MPaG.Thereafter, propylene was supplied to control the pressure to 0.60 MPaG.

The whole amount of a solution of 0.5 mL of the catalyst solution in 4.5mL of toluene was added to the autoclave, and polymerization wasperformed at 70° C. for 10 minutes. During the polymerization, propylenewas supplied to maintain the autoclave inside pressure at 0.60 MPaG. Thepolymerization was terminated by adding methanol to the autoclave. Therest of the procedure was the same as in Example 1D. The results aredescribed in Table 6.

Comparative Example 1D

Polymerization was performed by the same process as in Example 3D,except that the transition metal compound in Example 3D was changed to3.2 mg of the catalyst b, and the amount of methylaluminoxane (TMAO-341)was changed to 0.30 mL. The results are described in Table 6.

Comparative Example 2D

Polymerization was performed by the same process as in Example 2D,except that the transition metal compound in Example 2D was changed to2.9 mg of the catalyst a, and the amount of methylaluminoxane (TMAO-341)was changed to 0.30 mL. The results are described in Table 6.

TABLE 6 4-Methyl-1-pentene/propylene copolymerization Polymer- izationPolymer- Catalytic Amount of Propylene Amount of temper- ization Yieldactivity Propylene catalyst pressure hydrogen ature time amount kg/mmol-content [η] Tm Tc Example Catalyst μmol MPaG NL ° C. min g Zr/h mol %dl/g ° C. ° C. Ex. 1D Catalyst C 1.4 0.20 0.00 70 20 2.54 5.0 16.4 2.31134.2  85.9 Ex. 2D Catalyst C 4.1 0.10 0.00 70 20 30.98 2.3 × 10¹ 7.13.18 190.9 159.4 Ex. 3D Catalyst C 2.8 0.05 0.00 70 20 3.27 3.0 5.6 2.37216.3 189.5 Ex. 4D Catalyst D 0.22 0.10 0.13 70 10 53.66 1.5 × 10³ 8.02.36 189.3 157.9 Ex. 5D Catalyst D 0.22 0.10 0.06 80 10 37.60 1.0 × 10³Not 2.36 188.4 157.5 measured Ex. 6D Catalyst D 1.9 0.25 0.00 70 2016.65 2.7 × 10¹ Not 3.50 Not Not measured detected detected Ex. 7DCatalyst D 1.9 0.30 0.00 70 20 15.63 2.5 × 10¹ 22.8 3.51 Not Notdetected detected Ex. 8D Catalyst A 3.7 0.10 0.00 70 20 10.99 8.0 6.83.22 197.1 167.5 Ex. 9D Catalyst E 3.8 0.40 0.00 70 20 74.30 5.9 × 10¹Not 3.11 Not Not measured detected detected Ex. 10D Catalyst E 0.55 0.400.06 70 10 80.10 8.7 × 10² Not 1.81 Not Not measured detected detectedComp. Catalyst b 3.9 0.05 0.00 70 20 20.50 1.6 × 10¹ 5.0 1.60 194.9167.6 Ex. 1D Comp. Catalyst a 3.8 0.10 0.00 70 20 9.00 7.0 9.3 1.78179.8 149.2 Ex. 2D

Example 1E

A 1,500 mL-volume SUS autoclave that had been purged with nitrogen wasloaded with 500 mL of 4-methyl-1-pentene, 250 mL of cyclohexane, 85 mLof 1-octene, and 1.5 mL of a 0.5 M toluene solution oftriisobutylaluminum. The autoclave was heated to 60° C. After theaddition of 0.09 NL of hydrogen to the autoclave, nitrogen was suppliedto control the autoclave inside pressure to 0.10 MPaG. There wassupplied a toluene solution of a mixture including 0.11 μmol of atransition metal compound (the catalyst D) and 0.03 mmol ofmethylaluminoxane (TMAO-341) (Al/Zr=310 by mol), and polymerization wasperformed at 60° C. for 20 minutes. The polymerization was terminated byadding methanol to the autoclave. The resultant polymer solution wasadded to 2 L of a methanol-acetone mixed solvent (1:1 by volume) andthereby the polymer was precipitated. The polymer was dried underreduced pressure at 80° C. for 12 hours. The amount of the polymerobtained was 16.7 g. The results are described in Table 7-1.

Example 2E

A 1,500 mL-volume SUS autoclave that had been purged with nitrogen wasloaded with 750 mL of 4-methyl-1-pentene and 1.5 mL of a 0.5 M toluenesolution of triisobutylaluminum. The autoclave was heated to 70° C.After the addition of 0.06 NL of hydrogen to the autoclave, nitrogen wassupplied to control the autoclave inside pressure to 0.40 MPaG.Propylene was supplied to control the pressure to 0.50 MPaG. There wassupplied a toluene solution of a mixture including 0.22 μmol of atransition metal compound (the catalyst D) and 0.07 mmol ofmethylaluminoxane (TMAO-341) (Al/Zr=310 by mol), and polymerization wasperformed at 70° C. for 18.5 minutes. During the polymerization,propylene was supplied to maintain the autoclave inside pressure at 0.50MPaG. The polymerization was terminated by adding methanol to theautoclave. The rest of the procedure was the same as in Example 1E. Theamount of the polymer obtained was 50.9 g. The results are described inTable 7-1.

Example 3E

A 1,500 mL-volume SUS autoclave that had been purged with nitrogen wasloaded with 500 mL of 4-methyl-1-pentene, 250 mL of cyclohexane, 10.4 mLof LINEALENE 168 manufactured by Idemitsu Kosan Co., Ltd., and 1.5 mL ofa 0.5M toluene solution of triisobutylaluminum. LINEALENE 168 was ana-olefin mixture including 1-hexadecene and 1-octadecene. The autoclavewas heated to 60° C. After the addition of 0.13 NL of hydrogen to theautoclave, nitrogen was supplied to control the autoclave insidepressure to 0.14 MPaG. There was supplied a toluene solution of amixture including 0.11 μmol of a transition metal compound (the catalystD) and 0.04 mmol of methylaluminoxane (TMAO-341) (Al/Zr=310 by mol), andpolymerization was performed at 60° C. for 20 minutes. Thepolymerization was terminated by adding methanol to the autoclave. Therest of the procedure was the same as in Example 1E. The amount of thepolymer obtained was 54.7 g. The results are described in Table 7-1.

Example 4E

A 1,500 mL-volume SUS autoclave that had been purged with nitrogen wasloaded with 750 mL of 4-methyl-1-pentene, 26 mL of 1-octene, and 1.5 mLof a 0.5 M toluene solution of triisobutylaluminum. The autoclave washeated to 50° C. After the addition of 0.25 NL of hydrogen to theautoclave, nitrogen was supplied to control the autoclave insidepressure to 0.14 MPaG. There was supplied a toluene solution of amixture including 0.06 μmol of a transition metal compound (the catalystD) and 0.02 mmol of methylaluminoxane (TMAO-341) (Al/Zr=310 by mol), andpolymerization was performed at 50° C. for 15 minutes. Thepolymerization was terminated by adding methanol to the autoclave. Therest of the procedure was the same as in Example 1E. The amount of thepolymer obtained was 45.5 g. The results are described in Table 7-1.

Example 5E

A 1,500 mL-volume SUS autoclave that had been purged with nitrogen wasloaded with 500 mL of 4-methyl-1-pentene, 250 mL of cyclohexane, 9.8 mLof 1-decene, and 1.5 mL of a 0.5 M toluene solution oftriisobutylaluminum. The autoclave was heated to 60° C. After theaddition of 0.13 NL of hydrogen to the autoclave, nitrogen was suppliedto control the autoclave inside pressure to 0.14 MPaG. There wassupplied a toluene solution of a mixture including 0.11 μmol of atransition metal compound (the catalyst D) and 0.04 mmol ofmethylaluminoxane (TMAO-341) (Al/Zr=310 by mol), and polymerization wasperformed at 60° C. for 20 minutes. The polymerization was terminated byadding methanol to the autoclave. The rest of the procedure was the sameas in Example 1E. The amount of the polymer obtained was 49.0 g. Theresults are described in Table 7-1.

Example 6E

A 1,500 mL-volume SUS autoclave that had been purged with nitrogen wasloaded with 750 mL of 4-methyl-1-pentene and 1.5 mL of a 0.5 M toluenesolution of triisobutylaluminum. The autoclave was heated to 70° C.After the addition of 0.06 NL of hydrogen to the autoclave, nitrogen wassupplied to control the autoclave inside pressure to 0.50 MPaG. Therewas supplied a toluene solution of a mixture including 0.11 μmol of atransition metal compound (the catalyst D) and 0.04 mmol ofmethylaluminoxane (TMAO-341) (Al/Zr=310 by mol), and polymerization wasperformed at 70° C. for 20 minutes. The polymerization was terminated byadding methanol to the autoclave. The rest of the procedure was the sameas in Example 1E. The amount of the polymer obtained was 29.6 g. Theresults are described in Table 7-1.

Comparative Example 1E

A 1,500 mL-volume SUS autoclave that had been purged with nitrogen wasloaded with 750 mL of 4-methyl-1-pentene and 1.5 mL of a 0.5 M toluenesolution of triisobutylaluminum. The autoclave was heated to 70° C.Nitrogen was supplied to control the autoclave inside pressure to 0.40MPaG, and propylene was supplied to control the pressure to 0.50 MPaG.There was supplied a toluene solution of a mixture including 3.87 μmolof a transition metal compound (the catalyst b) and 1.17 mmol ofmethylaluminoxane (TMAO-341) (Al/Zr=310 by mol), and polymerization wasperformed at 70° C. for 20 minutes. During the polymerization, propylenewas supplied to maintain the autoclave inside pressure at 0.50 MPaG. Thepolymerization was terminated by adding methanol to the autoclave. Therest of the procedure was the same as in Example 1E. The amount of thepolymer obtained was 20.5 g. The results are described in Table 7-2.

Comparative Example 2E

A 1,500 mL-volume SUS autoclave that had been purged with nitrogen wasloaded with 500 mL of 4-methyl-1-pentene, 250 mL of cyclohexane, 5.0 mLof LINEALENE 168 manufactured by Idemitsu Kosan Co., Ltd., and 1.5 mL ofa 0.5 M toluene solution of triisobutylaluminum. The autoclave washeated to 50° C. Nitrogen was supplied to control the autoclave insidepressure to 0.16 MPaG. There was supplied a toluene solution of amixture including 11 μmol of a transition metal compound (the catalystb) and 1.17 mmol of methylaluminoxane (TMAO-341) (Al/Zr=100 by mol), andpolymerization was performed at 50° C. for 40 minutes. Thepolymerization was terminated by adding methanol to the autoclave. Therest of the procedure was the same as in Example 1E. The amount of thepolymer obtained was 43.2 g. The results are described in Table 7-2.

Comparative Example 3E

A 1,500 mL-volume SUS autoclave that had been purged with nitrogen wasloaded with 500 mL of 4-methyl-1-pentene, 250 mL of cyclohexane, 7.5 mLof 1-octene, and 1.5 mL of a 0.5 M toluene solution oftriisobutylaluminum. The autoclave was heated to 50° C. Nitrogen wassupplied to control the autoclave inside pressure to 0.16 MPaG. Therewas supplied a toluene solution of a mixture including 3.87 μmol of atransition metal compound (the catalyst b) and 1.17 mmol ofmethylaluminoxane (TMAO-341) (Al/Zr=310 by mol), and polymerization wasperformed at 50° C. for 20 minutes. The polymerization was terminated byadding methanol to the autoclave. The rest of the procedure was the sameas in Example 1E. The amount of the polymer obtained was 11.1 g. Theresults are described in Table 7-2.

Comparative Example 4E

A 1,500 mL-volume SUS autoclave that had been purged with nitrogen wasloaded with 500 mL of 4-methyl-1-pentene, 250 mL of cyclohexane, 3.5 mLof 1-decene, and 1.5 mL of a 0.5 M toluene solution oftriisobutylaluminum. The autoclave was heated to 50° C. Nitrogen wassupplied to control the autoclave inside pressure to 0.16 MPaG. Therewas supplied a toluene solution of a mixture including 3.87 μmol of atransition metal compound (the catalyst b) and 1.17 mmol ofmethylaluminoxane (TMAO-341) (Al/Zr=310 by mol), and polymerization wasperformed at 50° C. for 20 minutes. The polymerization was terminated byadding methanol to the autoclave. The rest of the procedure was the sameas in Example 1E. The amount of the polymer obtained was 19.8 g. Theresults are described in Table 7-2.

Comparative Examples 5E to 8E

The following TPX polymers (methyl pentene polymers) manufactured byMitsui Chemicals, Inc. were used as titanium-catalyzed 4-methylpentene-1copolymers. The results are described in Table 7-2.

Comparative Example 5E: MX002 (MFR=21 g/10 min, Tm=224° C.) ComparativeExample 6E: MX004 (MFR=26 g/10 min, Tm=228° C.) Comparative Example 7E:RT18 (MFR=25 g/10 min, Tm=233° C.) Comparative Example 8E: MX019 (MFR=90g/10 min, Tm=243° C.)

TABLE 7-1 Example Ex. 1E Ex. 2E Ex. 3E Ex. 4E Ex. 5E Ex. 6E Polymer-Catalyst Catalyst Catalyst Catalyst Catalyst Catalyst Catalyst ization DD D D D D conditions Comonomer 1-Octene Propylene LINEALENE 1-Octene1-Decene — 168 Composition Amount of mol 16 7.4 1.2 4 1.7 0 comonomer %Stereo- Meso diad % Fraction r Fraction r Fraction r Fraction r Fractionr Fraction r regularity fraction (m) was below was below was below wasbelow was below was below detection detection detection detectiondetection detection limit. limit. limit. limit. limit. limit. Thermal Tm° C. 153 191 221 220 234 243 Properties Tc ° C. 119 156 189 190 210 215Heat of fusion J/g 17 25 36 40 50 55 ΔHm (2nd) 0.5 × Tm − 76 J/g 0.519.5 34.5 34 41 45.5 Relation (1) Y Y Y Y Y Y Molecular [η] dl/g 2.7 2.42.5 2.4 2.2 2.4 weight Mechanical Young's MPa 1500 1300 1400 1600 2000properties modulus Elongation % 200 200 180 130 100 at break Izod kJ/m25 6 7 10 8 impact strength of unnotched specimen Heat Vicat softening °C. 150 170 170 190 200 resistance temperature Relation (1): Y = Thepolymer satisfied the relation (1). N = The polymer did not satisfy therelation (1).

TABLE 7-2 Comparative Example Comp. Ex. Comp. Ex. Comp. Ex. Comp. Ex.Comp. Ex. Comp. Ex. Comp. Ex. Comp. Ex. 1E 2E 3E 4E 5E 6E 7E 8E Polymer-Catalyst Catalyst Catalyst Catalyst Catalyst Ti Ti Ti Ti ization b b b bcatalyst catalyst catalyst catalyst conditions Comonomer PropyleneLINEALENE 1-Octene 1-Decene LINEALENE LINEALENE 1-Decene — 168 168 168Composition Amount of mol 8 0.6 2.5 1 2.8 2 1.9 0 comonomer % Stereo-Meso diad % 97.5 97.4 97.6 97.1 98 98.2 97.5 97.9 regularity fraction(m) Thermal Tm ° C. 181 220 218 230 224 228 233 243 properties Tc ° C.148 190 188 205 207 210 214 218 Heat of fusion J/g 13 27 29 33 23 30 3945 ΔHm (2nd) 0.5 × Tm − 76 J/g 14.5 34 33 39 36 38 40.5 45.5 Relation(1) N N N N N N N N Molecular [η] dl/g 1.6 2.1 2.2 1.9 2.2 2.2 2.2 2.4weight Mechanical Young's MPa 1000 830 950 1200 800 1200 1400 1800properties modulus Elongation % 190 190 150 100 370 80 40 10 at breakIzod kJ/m2 3 3 3 2 Not 15 9 4 impact broken strength of unnotchedspecimen Heat Vicat softening ° C. 130 163 162 175 140 155 170 185resistance temperature Relation (1): Y = The polymer satisfied therelation (1). N = The polymer did not satisfy the relation (1).

The properties in Table 7-1 and Table 7-2 were evaluated as follows.

<Tensile test (Compression molded sheets)>

To evaluate tensile properties, namely, Young's modulus (YM) andelongation at break (EL), a JIS K 7113 No. 2 test piece 1/2 that hadbeen punched out from a 1 mm thick compression molded sheet obtained asdescribed below was used as an evaluation sample and was tested at 23°C. and a tension rate of 200 mm/min.

Compression molding conditions: With a hydraulic hot compression moldingmachine manufactured by Shinto Metal Industries Corporation, theworkpiece was heated at 270° C. under a pressure of 10 MPa for 5 minutesand was cooled at 30° C. under a pressure of 10 MPa for 5 minutes.

<Izod impact test (Compression molded sheets)>

A 3 mm thick compression molded sheet fabricated as described below wassubjected to an impact test in accordance with Izod ASTM underconditions in which the hammer energy was 3.92 J, the swing angle was149.1° and the test temperature was 23° C.

Compression molding conditions: With a hydraulic hot compression moldingmachine manufactured by Shinto Metal Industries Corporation, theworkpiece was heated at 270° C. under a pressure of 10 MPa for 5 minutesand was cooled at 30° C. under a pressure of 10 MPa for 5 minutes.

<Vicat softening temperature (Compression molded sheets)>

A 3 mm thick compression molded sheet fabricated as described below wassubjected to a Vicat softening temperature test in accordance with ASTMD1525 at a heating rate of 50° C./hr and a testing load of 10 N using atester manufactured by Yasuda Seiki Seisakusho Ltd.

Compression molding conditions: With a hydraulic hot compression moldingmachine manufactured by Shinto Metal Industries Corporation, theworkpiece was heated at 270° C. under a pressure of 10 MPa for 5 minutesand was cooled at 30° C. under a pressure of 10 MPa for 5 minutes.

<Evaluations>

In the studies described in Table 7-1, the Young's modulus as anindicator of rigidity was high and the elongation at break as anindicator of toughness was approximately of the same level asconventional products. On the other hand, the studies described in Table7-2 resulted in poor Young's modulus. The values of Young's modulusdescribed in Table 7-1 and Table 7-2 are plotted versus elongation atbreak in FIG. 2.

Based on the results described in Table 7-1 and Table 7-2, the heat offusion (ΔHm) is plotted versus melting point (Tm) in FIG. 3. The resultsin Table 7-1 and Table 7-2 (FIG. 2 and FIG. 3) show that the polymerswith an excellent balance between rigidity and toughness have a largerΔHm than the polymers with similar toughness but with poor rigidity whenthe polymers having similar melting points Tm are compared.

In crystalline polymers, Tm and ΔHm are generally in an approximatelyproportional relationship. Thus, it will be possible to draw alinebetween 4MP1 polymers with an excellent rigidity/toughness balance(written as “Examples” for convenience) and 4MP1 polymers with similartoughness but with poor rigidity (written as “Comparative Examples” forconvenience) in FIG. 3 based on the values of Tm and ΔHm in the abovestudies. A numerical analysis was then made with respect to such a lineso as to fit the line between the data of Examples and the data ofComparative Examples, resulting in ΔHm=0.5×Tm−76.

From the comparison of the polymers described in Table 7-1 and Table7-2, it is understood that the polymers achieve an excellent balancebetween rigidity and toughness when the polymers satisfy the relation(1): ΔHm≦0.5×Tm−76.

Example 1F

A 1,500 mL-volume SUS autoclave that had been purged with nitrogen wasloaded with 750 mL of 4-methyl-1-pentene and 1.5 mL of a 0.5 M toluenesolution of triisobutylaluminum. The autoclave was heated to 70° C.After the addition of 0.13 NL of hydrogen to the autoclave, nitrogen wassupplied to control the autoclave inside pressure to 0.20 MPaG.Propylene was supplied to control the pressure to 0.60 MPaG. There wassupplied a toluene solution of a mixture including 0.22 μmol of atransition metal compound (the catalyst D) and 0.07 mmol ofmethylaluminoxane (TMAO-341) (Al/Zr=310 by mol), and polymerization wasperformed at 70° C. for 10 minutes. During the polymerization, propylenewas supplied to maintain the autoclave inside pressure at 0.60 MPaG. Thepolymerization was terminated by adding methanol to the autoclave. Therest of the procedure was the same as in Example 2E. The amount of thepolymer obtained was 53.2 g. The results are described in Table 8.

Example 2F

A 1,500 mL-volume SUS autoclave that had been purged with nitrogen wasloaded with 750 mL of 4-methyl-1-pentene and 1.5 mL of a 0.5 M toluenesolution of triisobutylaluminum. The autoclave was heated to 70° C.Nitrogen was supplied to control the autoclave inside pressure to 0.20MPaG, and propylene was supplied to control the pressure to 0.60 MPaG.There was supplied a toluene solution of a mixture including 3.8 μmol ofa transition metal compound (the catalyst D) and 1.18 mmol ofmethylaluminoxane (TMAO-341) (Al/Zr=310 by mol), and polymerization wasperformed at 70° C. for 20 minutes. During the polymerization, propylenewas supplied to maintain the autoclave inside pressure at 0.60 MPaG. Thepolymerization was terminated by adding methanol to the autoclave. Therest of the procedure was the same as in Example 2E. The amount of thepolymer obtained was 63.0 g. The results are described in Table 8.

Comparative Example 1F

A 1,500 mL-volume SUS autoclave that had been purged with nitrogen wasloaded with 400 mL of 4-methyl-1-pentene, 300 mL of hexane, and 0.75 mLof a 1.0 M toluene solution of triisobutylaluminum. The autoclave washeated to 60° C., and propylene was supplied to control the autoclaveinside pressure to 0.40 MPaG. There was supplied a toluene solution of amixture including 10 μmol of a transition metal compound (the catalystb) and 1.00 mmol of methylaluminoxane (TMAO-341) (Al/Zr=100 by mol), andpolymerization was performed at 60° C. for 60 minutes. During thepolymerization, propylene was supplied to maintain the autoclave insidepressure at 0.40 MPaG. The polymerization was terminated by addingmethanol to the autoclave. The rest of the procedure was the same as inExample 1E. The results are described in Table 8. The amount of thepolymer obtained was 36.9 g.

TABLE 8 Comp. Ex. 1F Ex. 2F Ex. 1F Polymeriza- Catalyst CatalystCatalyst Catalyst tion D D b conditions Comonomer Propylene PropylenePropylene Composition Amount of mol 28 27 28 comonomer % Stereo- Mesodiad % Fraction Fraction 97.5 regularity fraction (m) r was r was belowbelow detection detection limit. limit. Thermal Tm ° C. Not Not Notproperties detected detected detected Tc ° C. Not Not Not detecteddetected detected Heat of fusion J/g Not Not Not ΔHm (2nd) detecteddetected detected Molecular [η] dl/g 1.5 3.2 1.5 weight VibrationMaximum — 2.8 2.8 2.7 damping value of properties loss tan- gent (tanδ)Rubber Permanent — 9.9 8.2 13.4 elasticity tensile elongation (150%)Strain Permanent % 38 23 45 recovery compression set (23° C.) Gelfraction % Not more Not more Not more than 0.5 than 0.5 than 0.5

The properties in Table 8 were evaluated as follows.

<Loss tangent tanδ(Compression molded sheets)>

A 3 mm thick compression molded sheet was fabricated under the followingconditions and was cut to give a 45 mm×10 mm×3 mm rectangular piece fordynamic viscoelasticity measurement. With MCR301 manufactured by ANTONPaar, the temperature dependency of dynamic viscoelasticity was measuredat a frequency of 10 rad/s in the range of −70 to 180° C. The maximumvalue of loss tangent (tanδ) at the glass transition temperature wasobtained.

Compression molding conditions: With a hydraulic hot compression moldingmachine manufactured by Shinto Metal

Industries Corporation, the workpiece was heated at 200° C. under apressure of 10 MPa for 5 minutes and was cooled at 30° C. under apressure of 10 MPa for 5 minutes.

<Permanent tensile elongation (150%)>

A 1 mm thick compression molded sheet was fabricated under the followingconditions, and a JIS K7113 No. 2 test piece 1/2 was punched out fromthe compression molded sheet as an evaluation sample. The test piece wasstretched by 150% at a tension rate of 30 mm/min, and the distancebetween the chucks was measured. The test piece was held at 23° C. for10 minutes. After 10 minutes after the stress was released, the distancebetween the chucks on the test piece was measured. The differencebetween the distances was obtained as the permanent tensile elongation.

Compression molding conditions: With a hydraulic hot compression moldingmachine manufactured by Shinto Metal Industries Corporation, theworkpiece was heated at 200° C. under a pressure of 10 MPa for 5 minutesand was cooled at 30° C. under a pressure of 10 MPa for 5 minutes.

<Permanent compression set (Compression molded sheets)>

A 3 mm thick compression molded sheet was fabricated under theconditions described below. Four such sheets were stacked on top of oneanother, and the resultant 12 mm thick sample was compressed by 25% andwas heat treated at 23° C. for 22 hours in accordance with JIS K6262.After the sample was allowed to stand at 23° C. for 2 hours, thethickness was measured. The amount of strain calculated from thedifference in thickness between before and after the test was taken asthe permanent compression set.

Compression molding conditions: With a hydraulic hot compression moldingmachine manufactured by Shinto Metal Industries Corporation, theworkpiece was heated at 200° C. under a pressure of 10 MPa for 5 minutesand was cooled at 30° C. under a pressure of 10 MPa for 5 minutes.

<Evaluations>

The polymers obtained in Examples 1F and 2F had a meso diad fraction (m)of not less than 98.5%, and did not show a melting point Tm. Asdescribed in Table 8, these polymers exhibited a small permanentcompression set in spite of the fact that the loss tangent wasapproximately the same as the polymer in Comparative Example 1F. Thatis, it has been demonstrated that the novel amorphous 4-methyl-1-pentenepolymers of the invention have an excellent balance of viscoelasticproperties.

4-Methyl-1-pentene polymerization using supported catalysts

Example 1G (1) Preparation of Supported Catalyst Using Catalyst D

8.5 kg of a silica (SUNSPHERE H-31 manufactured by AGC Si-Tech Co.,Ltd.) that had been dried at 200° C. for 3 hours was suspended into 33 Lof toluene. Thereafter, 124.5 L of a toluene solution ofmethylaluminoxane (Al=1.42 mol/L) was added dropwise over a period of 30minutes. The temperature was then increased to 115° C. in 1.5 hours, andreaction was performed at the temperature for 4 hours. Thereafter, thetemperature was decreased to 60° C., and the supernatant liquid wasremoved by decantation. The resultant solid catalyst component waswashed with toluene three times, and was resuspended into toluene (0.16g/mL, 1.5 mmol-Al/mL). Thus, a silica-supported methylaluminoxane(MAO/Si=1.25 by mol) was obtained.

In a 100 mL three-necked flask that had been thoroughly purged withnitrogen, 4.5 mmol in terms of aluminum of the silica-supportedmethylaluminoxane was added and was suspended by the addition of 39 mLof toluene. To the suspension, 15.5 mg (18 μmol) of the transition metalcompound (the catalyst

D) synthesized in [Synthetic Example 4] was added in the form of atoluene solution (2.3 mmol/L). Stirring was stopped after 1 hour, andthe suspension was washed by decantation three times, and thereby thesolvent was replaced by decane. Next, 2.0 mmol of diisobutylaluminumhydride (as a 1.0 mmol/mL decane solution) was added, and further3-methyl-1-pentene (2.2 mL) was added. Stirring was stopped after 1hour, and the suspension was washed by decantation three times. Thus, acatalyst suspension (a 5 g/L decane slurry, 0.18 mmol-Zr/L) wasobtained.

(2) 4-Methyl-1-pentene polymerization

In a stream of nitrogen, 300 mL of 4-methyl-1-pentene was added to a 500mL-volume glass polymerization reactor at room temperature. Thetemperature was increased. A mixed gas of 0.5 L/h hydrogen and 15 L/hnitrogen was passed. Further, 0.1 mmol of triisobutylaluminum (as a 1.0mmol/mL decane solution) and 0.001 mmol in terms of zirconium atoms ofthe catalyst suspension prepared above were added. Stirring wasperformed while maintaining the inside of the polymerization reactor at40° C. After the polymerization was performed for 1 hour, isobutylalcohol was added into the polymerization reactor to terminate thepolymerization. Immediately thereafter, the polymerization liquid wasfiltered and thereby a solid polymer was obtained. Drying under reducedpressure at 80° C. for 8 hours resulted in 11.0 g of the polymer. Thepolymer had an intrinsic viscosity [η] of 5.58 dl/g and Tm of 242.6° C.The soluble proportion (SP) was 0.38 wt %.

Comparative Example 1G

The polymerization of 4-methyl-1-pentene was carried out in the samemanner as in Example 1G, except that the catalyst in the catalystsuspension was prepared from 12.5 mg (17 μmol) of the transition metalcompound (the catalyst d) of Comparative Synthetic Example 4 and 4.6mmol in terms of aluminum of the silica-supported methylaluminoxane, andthat the polymerization involved the catalyst in an amount of 0.4 mmolin terms of zirconium atoms. The amount of the polymer obtained was 5.8g. The polymer had an intrinsic viscosity [_(i)] of 1.50 dl/g and Tm of232.8° C. The soluble proportion (SP) was 17 wt %.

INDUSTRIAL APPLICABILITY

The olefin polymer production processes of the invention can produceuseful olefin polymers having high heat resistance and high molecularweight in an economically efficient manner. Thus, the productionprocesses of the invention are highly valuable in industry. Further, thenovel 1-butene polymers and 4-methyl-1-pentene polymers of the inventionhave various excellent properties.

1-12. (canceled)
 13. A 1-butene polymer which has a meso pentad fractionas measured by ¹³C-NMR of 98.0% to 99.8%.
 14. The 1-butene polymeraccording to claim 13, wherein the accumulated elution amount at atemperature [T_(X)] is 40% by weight or more relative to the wholeelution amount as measured by cross fractionation chromatography (CFC)using o-dichlorobenzene as an eluent, provided that [T_(X)] is definedas ([T_(S)]+[T_(E)])/2 wherein [T_(S)] is an elution start temperature(a temperature at which the accumulated elution weight percent reaches0.5% by weight), and [T_(E)] is an elution end temperature (atemperature at which the accumulated elution weight percent reaches 99%by weight). 15-16. (canceled)
 17. The 1-butene polymer according toclaim 13, wherein the meso pentad fraction as measured by ¹³C-NMR is inthe range of 98.3% to 99.8%.
 18. The 1-butene polymer according to claim13, wherein the total of the proportion of regioerrors due to2,1-insertions of 1-butene monomers and the proportion of regioerrorsdue to 1,4-insertions in all the 1-butene constituent units measured by¹³C-NMR spectroscopy is not more than 0.1 mol %.
 19. The 1-butenepolymer according to claim 13, which has a molecular weight distribution(Mw/Mn) of 1.5 to 5.0.